Comptes Rendus Chimie

Ali Amoozadeh

Elham Tabrizian

Salman Rahmani

Comptes Rendus
Chimie
Ali Amoozadeh, Elham Tabrizian and Salman Rahmani
Erratum to: “Nano titania-supported sulfonic acid catalyzed synthesis of
α,α′-bis(substituted-benzylidene)cycloalkanones and their xanthene derivatives
under solvent-free conditions”
Volume 27 (2024), p. 111
Online since: 17 April 2024
https://doi.org/10.5802/crchim.289
This article is licensed under the
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Comptes Rendus. Chimie
2024, Vol. 27, p. 111
https://doi.org/10.5802/crchim.289
Erratum
Erratum to: “Nano titania-supported sulfonic acid
catalyzed synthesis of
α,α′-bis(substituted-benzylidene)cycloalkanones
and their xanthene derivatives under solvent-free
conditions”
Ali Amoozadeh ,∗,a, Elham Tabrizian ,a and Salman Rahmani ,a
a Department of Chemistry, Semnan University, Semnan 3535119111, Iran
E-mail: aamozadeh@semnan.ac.ir (A. Amoozadeh)
This note corrects the article “Nano titania-
supported sulfonic acid catalyzed synthesis of α,α′-
bis(substituted-benzylidene)cycloalkanones and their
xanthene derivatives under solvent-free conditions”
published online in Comptes Rendus Chimie on
16 May 2015, Volume 18 (2015), no. 8, https:
//doi.org/10.1016/j.crci.2014.11.003.
The authors regret that in the original publica-
tion of their article, the image displayed as Fig-
ure 2 was incorrect. The proper figure is avail-
able in this erratum. The authors deeply apologize
for this inadvertent mistake and any inconvenience
caused.
Figure 2. SEM images of n-TSA before use (a) and after reuse seven times (b).
∗Corresponding author.
ISSN (electronic) : 1878-1543 https://comptes-rendus.academie-sciences.fr/chimie/


Erratum to: “Nano titania-supported sulfonic acid catalyzed synthesis of α,α′-bis(substituted-benzylidene)cycloalkanones and their xanthene derivatives under solvent-free conditions”

Janine Cossy

Comptes Rendus
Chimie
Janine Cossy
A Collection of Articles Highlighting Women Chemists in France in 2024
Volume 27, Special Issue S2 (2024), p. 3
Online since: 17 April 2024
Issue date: 11 July 2024
Part of Special Issue: Women Chemists in France in 2024
Guest editor: Janine Cossy (ESPCI Paris – PSL, CNRS, 75005 Paris, France)
https://doi.org/10.5802/crchim.302
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http://creativecommons.org/licenses/by/4.0/
C EN T R E
MER S ENN E
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Mersenne Center for open scientific publishing
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Comptes Rendus. Chimie
2024, Vol. 27, Special issue S2, p. 3
https://doi.org/10.5802/crchim.302
Foreword
Women Chemists in France in 2024
A Collection of Articles Highlighting Women
Chemists in France in 2024
Janine Cossy
Women in science are achieving groundbreaking
research across the world. But despite their involve-
ment, their dedication to research, and their discov-
eries, women still represent only around 33% of re-
searchers, and less than 4% of Nobel Prizes for sci-
ence have been awarded to women. In addition, only
11% of senior research roles are held by women in Eu-
rope. Their work rarely gains the recognition it de-
serves.
However, different institutions and organizations
are fighting to encourage women to take a scientific
career, to recognize their merits in sciences (IUPAC,
L’Oreal, UNESCO, UN etc.) and to advocate the cause
of women in science. We can cite Audrey Azoulay,
General Director of the United Nations Educational
Scientific and Cultural Organization, who said “by
advancing the cause of women, we can drive progress
in science”.
If, in 2024, we still have special prizes to help
empower more women scientists and to recognize
women’s scientific excellence, this means that we
still have a lot of work to do to reach gender equal-
ity and to encourage young girls to pursue a sci-
entific career. Women scientists still need to fight
to be judged purely on the merit of their discover-
ies and the potential of their work to change the
world.
In this context, the editorial board of the Compte
Rendus Chimie of the Academy of Sciences has de-
cided to have a special issue to highlight the scientific
achievements of women chemists in France in dif-
ferent areas of chemistry and to encourage younger
generations to pursue careers in chemistry. This is-
sue brings together 12 outstanding contributions in
different fields of chemistry.
In 2025, a second issue is planned and we do hope
that the Compte Rendus of the Academy of Sciences
will act as spokespersons for women scientists in
France in various fields.
For this 2024 special issue, I would like to thank
P. Braunstein for enthusiastically accepting my pro-
posals, Justine Fabre and Julien Desmarets for all
their help and advice in producing this special issue.
Thanks also to all the authors and co-authors for their
willingness to take part in the adventure. I hope that
this special issue will be a source of inspiration for
readers and that it will lead to new collaborations.
Janine Cossy
ESPCI Paris
PSL University
France
janine.cossy@espci.fr
ISSN (electronic): 1878-1543 https://comptes-rendus.academie-sciences.fr/chimie/


A Collection of Articles Highlighting Women Chemists in France in 2024

Arthur Lasbleiz

Franck Pelissier

Jean-Hugues Renault

Claire M. Grison

Yves-Marie Legrand

Claude Grison

A new generation of ecocatalysts$^{\text{®}}$—from Invasive Alien Species to sustainable and biosourced glyceryl fatty esters

Charly Mve Mfoumou

Pradel Tonda-Mikiéla

Francis Ngoye

Spenseur Bouassa Mougnala

Berthy Lionel Mbouiti

Guy Raymond Feuya Tchouya

Removal and adsorption kinetics of copper(II) ions from aqueous media on activated carbon in dynamic adsorption on a fixed-bed column

Damir A. Safin

Structural and in silico studies of 2-pyridyl-decorated 2-amino-1,3,5-triazine with a potency against SARS-CoV-2 proteins

Margrete Juel Henrichsen

Jesper Bendix

Høgni Weihe

Parallel-mode EPR spectra of the hexaaqua manganese(II) Ion in tetrahedral symmetry

Mathieu Berthelot

Julie Echaubard

Asmae Bousfiha

Charles H. Devillers

(Pyridin-2-ylmethyl)porphyrins: synthesis, characterization and C–N oxidative fusion attempts

Simon Larsen

Jeanet Conradie

Nicolas Desbois

Claude P. Gros

Abhik Ghosh

Comptes Rendus
Chimie
Simon Larsen, Jeanet Conradie, Nicolas Desbois, Claude P. Gros
and Abhik Ghosh
Hypsochlorins
Volume 27, Special Issue S1 (2024), p. 125-132
Online since: 19 March 2024
Issue date: 24 December 2024
Part of Special Issue: French/Nordic Special Issue on Materials and Coordination
Chemistry
Guest editors: Claude P. Gros (Université de Bourgogne, Dijon, France) and Abhik
Ghosh (The Arctic University, UiT, Tromsø, Norway)
https://doi.org/10.5802/crchim.299
This article is licensed under the
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C EN T R E
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Comptes Rendus. Chimie
2024, Vol. 27, Special issue S1, p. 125-132
https://doi.org/10.5802/crchim.299
Preliminary communication
French/Nordic Special Issue on Materials and Coordination Chemistry
Hypsochlorins
Simon Larsen ,a, Jeanet Conradie ,a,b, Nicolas Desbois ,c, Claude P. Gros ,∗,c and
Abhik Ghosh ,∗,a
a Department of Chemistry, UiT – The Arctic University of Norway, Tromsø N-9037,
Norway
b Department of Chemistry, University of the Free State, Bloemfontein 9300,
Republic of South Africa
c Institut de Chimie Moléculaire de l’Université de Bourgogne (ICMUB), UMR CNRS
6302, Université de Bourgogne, 9 Avenue Alain Savary, BP 47870, 21078 Dijon Cedex,
France
E-mails: claude.gros@u-bourgogne.fr (C. P. Gros), abhik.ghosh@uit.no (A. Ghosh)
Abstract. Both the Soret and Q bands of chlorin e6 complexes blueshift on going from Zn to Pd to
Pt as the coordinated metal, establishing the latter two complexes as hypsochlorins. DFT/TDDFT
calculations indicate that the blueshifts appear to be related to the presence of the electronegative
metal ion, which lowers the orbital energies of the HOMO and HOMO-1, while leaving the LUMOs
relatively unaffected.
Keywords. Chlorin, Hypsochlorin, Hypso, Hypsoporphyrin, TDDFT.
Funding. Research Council of Norway (Grant no. 262229), CNRS (Grant no. UMR UBCNRS 6302),
South African National Research Foundation (Grant nos. 129270 and 132504).
Manuscript received 29 September 2023, revised 10 January 2024, accepted 8 February 2024.
1. Introduction
Over a half-century ago, Martin Gouterman [1] de-
vised his eponymous four-orbital model of porphyrin
spectra, and thereby was able to classify them as be-
longing to three broad classes, normal, hyper and
hypso [2,3]. Briefly, hyper spectra exhibit redshifted
features and/or extra features relative to normal
spectra, while hypso spectra are blueshifted relative
to normal spectra. Although the variety of porphyri-
noid compounds is vastly greater today, Gouterman’s
classification remains useful. Thus, the hyperpor-
phyrin concept has emerged as a design principle
for photosensitizers for photodynamic therapy and
∗Corresponding authors
related applications [4]. Many hypsoporphyrins are
phosphorescent and potentially useful as triplet pho-
tosensitizers, in such applications as oxygen sensing
and photodynamic and related therapies [5–7]. The
hypso effect had long been attributed to an increase
in the HOMO–LUMO gap in certain late transition
porphyrins as a result of antibonding interactions
between occupied metal dπ orbitals and the por-
phyrin’s eg LUMOs. A recent DFT investigation, how-
ever, has indicated a different origin for the hypso ef-
fect, namely, a lowering of the a2u HOMOs in met-
alloporphyrins with relatively electronegative metal
ions such as Pd(II) and Pt(II) [8].
Many years ago, we showed that Gouterman’s
four-orbital model also applies to corroles [9,10].
Unsurprisingly, many metallocorroles exhibit hyper
spectra [11–13] and quite a few also exhibit hypso
ISSN (electronic): 1878-1543 https://comptes-rendus.academie-sciences.fr/chimie/
126 Simon Larsen et al.
Scheme 1. A chlorin e6 trimethyl ester metal
complex with partial atom numbering.
spectra [8]. Herein we show that the hypso effect also
applies to chlorins [14,15], with both the Soret and
Q band maxima of chlorins blueshifting, going from
Zn to Pd to Pt as the coordinated metal (Scheme 1).
The finding is surprising in that the HOMO of closed-
shell chlorins is invariably an a1u-type MO (in terms
of D4h irreps) [3,16–19] which has no amplitude on
the central nitrogen atoms and is, therefore, likely to
be unaffected by the electronegativity of the central
metal. Gratifyingly, the spectral data proved consis-
tent with electrochemical cyclic voltammetry mea-
surements and DFT/TDDFT calculations, leading to
a coherent picture of hypsochlorins, as described
below.
2. Results and discussion
Table 1 lists the UV–vis absorption maxima and redox
potentials (V versus SCE) of the Zn, Pd, and Pt com-
plexes of chlorin e6 trimethyl ester, M[Chl-e], where
M = Zn, Pd, and Pt; the UV–vis spectra and cyclic
voltammograms are depicted in Figures 1 and 2, re-
spectively. From Zn to Pd and from Pd to Pt, the
Q band blueshifts by 14 and 10 nm, respectively, and
Figure 1. UV–visible spectra of M[Chl-e],
where M = Zn, Pd, and Pt, in CH2Cl2 at ambi-
ent temperature.
the Soret by 8 and 10 nm, respectively. The two
minor features between the Soret and Q bands also
blueshift in the same order. All complexes exhibit
reversible 1st oxidations and 1st reductions. While
there are small variations in the 1st reduction po-
tentials there are greater variations in the 1st oxida-
tion potentials and a clear trend of increasing ox-
idation potentials in the order of Zn < Pd < Pt,
which in turn results in an increasing electrochemi-
cal HOMO–LUMO gap for the same series. The elec-
trochemical data thus suggests that the hypso effect
in chlorins stems primarily from a lowering of the
HOMO energy in the presence of an electronegative
coordinated metal.
To obtain a qualitative understanding of the above
findings, DFT and TDDFT calculations were carried
out using simple unsubstituted chlorin models of the
complexes studied. The OLYP [20,21]-D3 [22]/ZORA-
STO-TZ2P optimized geometries of M[Chl] (M =
Zn, Pd, Pt; Chl = unsubstituted chlorin; Figure 3)
revealed essentially planar (as opposed to ruffled)
geometries so differences in macrocycle conforma-
tion appear unlikely to be a significant contributor to
the observed spectral differences [23]. Single-point
CAMY-B3LYP [24] calculations were then carried
out on the OLYP-D3 geometries. Figure 4 depicts
selected CAMY-B3LYP frontier MOs along with
the corresponding orbital energies, while Figure 5
Simon Larsen et al. 127
Table 1. Redox potentials (V versus SCE) and UV–vis absorption maxima of the compounds studied
Compound E1/2ox2 E1/2ox1 E1/2red1 E1/2red2 Ered2 ∆E Soret band (nm) Q band (nm)
Zn[Chl-e] 0.96 0.55 −1.29 – −1.79 1.84 411 637
Pd[Chl-e] – 0.77 −1.17 −1.69 – 1.94 403 623
Pt[Chl-e] – 0.81 −1.22 −1.73 – 2.03 393 613
Figure 2. Cyclic voltammograms (V versus
SCE) of M[Chl-e], where M = Zn, Pd, and Pt, in
CH2Cl2 containing 0.1 M tetrabutylammonium
perchlorate at ambient temperature; scan rate
100 mV·s−1.
presents the orbital energy levels in a graphical
manner. Figure 6 depicts the simulated TD-CAMY-
B3LYP-D3/Q4 STO-TZ2P-COSMO optical spectra
in dichloromethane of the three M[Chl] deriva-
tives. The key result is that, while the LUMO and
LUMO+1 energies are essentially constant across
all three M[Chl] derivatives, both the HOMO and
HOMO-1 energies downshift going from Zn to Pd to
Pt. Understandably, the downshifts for the a1u-type
HOMO are smaller than those for the a2u-type
HOMO-1, given that only the latter has substantial
amplitudes on the central nitrogen atoms. In spite
of the simplicity of our models, these computational
results appear to nicely, if qualitatively, capture the
essence of both the UV–vis and electrochemical
measurements.
Finally, the calculated absorption maxima from
CAMY-B3LYP TDDFT calculations on M[Chl] in
dichloromethane (Figure 6) were found to be in
surprisingly good agreement with the experimental
absorption maxima for M[Chl-e]. Thus, for instance,
the calculations correctly captured the larger hyp-
sochromic shifts for the Q band relative to the Soret
band. In all three cases, the Q band consists of ap-
proximately 95% HOMO → LUMO character, with
the remainder made up of HOMO-1 → LUMO+1
character (Table 2). The Soret band, by compari-
son, consists of a mixture of HOMO-1 → LUMO and
HOMO → LUMO+1 character. Since both the HOMO
and HOMO-1 downshift from Zn through Pd to Pt,
it makes sense that both the Q and Soret absorption
maxima blueshift in the same order.
In summary, a combined experimental and the-
oretical study indicates the plausible occurrence of
a hypso effect in chlorins. Thus, both the Soret
and Q bands blueshift going from Zn to Pd to Pt
as the coordinated metal. As in the case of por-
phyrins, the blueshifts appear to be largely attrib-
utable to the presence of an electronegative coordi-
nated atom, which lowers the orbital energies of the
HOMO and HOMO-1, while leaving the LUMOs rela-
tively unaffected.
3. Experimental section
3.1. Materials
All reagents were purchased from Sigma-Aldrich
and used as received except chlorin e6 trimethyl
ester (CAS 35038-32-5) which was purchased from
PorphyChem. Silica gel 60 (0.04–0.063 mm parti-
cle size, 230–400 mesh, Merck) was employed for
flash chromatography. Silica gel 60 preparative thin-
layer chromatographic plates (20 cm × 20 cm ×
0.5 mm, Merck) were used for final purification of all
compounds.
3.2. General instrumental methods
UV–visible spectra were recorded on an HP 8454
spectrophotometer. 1H NMR spectra were recorded
128 Simon Larsen et al.
Figure 3. Selected skeletal bond distances for M[Chl], where M = Zn, Pd, and Pt and Chl = unsubstituted
chlorin.
on a 400 MHz Bruker Avance III HD spectrom-
eter equipped with a 5 mm BB/1H SmartProbe
and referenced to either residual C6H6 at 7.16 ppm
or residual CHCl3 at 7.26 ppm. High-resolution
electrospray-ionization mass spectra were recorded
on an Orbitrap Exploris 120 spectrometer using
methanolic solutions. Cyclic voltammetry was car-
ried out at ambient temperature with a Gamry Ref-
erence 620 potentiostat equipped with a three-
electrode system: a 3 mm disc glassy carbon work-
ing electrode, a platinum wire counter-electrode,
and a saturated calomel reference electrode (SCE).
Tetra(n-butyl)ammonium perchlorate (CAUTION!)
was used as the supporting electrolyte. Anhydrous
CH2Cl2 (Sigma-Aldrich) was used as solvent. The
electrolyte solution was purged with argon for at
least 2 min prior to all measurements, which were
carried out under an argon blanket. The glassy car-
bon working electrode was polished using a pol-
ishing pad and 0.05 micrometer polishing alumina
from ALS Japan. All potentials were referenced
to the SCE.
3.3. Synthesis
The Zn complex was made by adding a solution of
Zn(OAc)2 • 2H2O (29.5 mg, 4 eq.) in 1 mL MeOH
to a solution of chlorin e6 trimethyl ester (21.9 mg)
in 5 mL chloroform. The resulting solution was re-
fluxed for 1 h. The Pd complex was made by dissolv-
ing chlorin e6 trimethyl ester (17.3 mg) and Pd(OAc)2
(19.7 mg, 3 eq.) in 5 mL pyridine and refluxing the
resulting solution for 4 h. The Pt complex was made
by dissolving chlorin e6 trimethyl ester (18.0 mg) and
Pt(OAc)2 (26.3 mg, 3 eq.) in 5 mL benzonitrile and
refluxing the resulting solution for 10 h. Following
reflux, each mixture was rotary-evaporated to dry-
ness and the residue dissolved in DCM and placed
on a silica column. Dichloromethane/ethyl acetate
20:1 eluted a blue fraction which was evaporated to
Simon Larsen et al. 129
Figure 4. CAMY-B3LYP frontier MOs of M[Chl] (M = Zn, Pd, Pt), with C2 irreps (a and b) and orbital
energies.
dryness and further purified by preparative TLC us-
ing n-hexane/ethyl acetate 1:1 as solvent. Yields and
analytical details are as follows:
3.3.1. Zn[Chl-e]
Yield 16.8 mg, 70%. UV–Vis (CH2Cl2) λmax (nm)
[ϵ × 10−4 (M−1·cm−1)]: 411 (8.50), 505 (0.40), 593
(0.58), 637 (2.98). 1H NMR (400 MHz, C6D6, δ in
ppm): 9.54 (s, 1H, 5), 9.41 (s, 1H, 10), 8.50 (s, 1H,
20), 8.05 (dd, J = 17.8, 11.5 Hz, 1H, 31), 6.18 (d, J =
18.0 Hz, 1H, 32 trans), 5.91 (d, J = 1.8 Hz, 1H, 32 cis),
5.45 (d, J = 19.0 Hz, 1H, 151), 5.28 (d, J = 19.0 Hz, 1H,
151), 4.28 (d, J = 10.2 Hz, 1H, 17), 4.01 (t, J = 7.1 Hz,
1H, 18), 3.95 (s, 3H, OCH3), 3.59 (s, 3H, OCH3), 3.47
(q, J = 7.5 Hz, 2H, 81), 3.38 (s, 3H, OCH3), 3.26 (s,
3H, 121), 3.25 (s, 3H, 21), 3.01 (s, 3H, 71), 2.30 (dt, J =
15.9, 7.9 Hz, 1H, 171), 2.07 (d, J = 10.0 Hz, 1H, 171),
2.00–1.91 (m, 1H, 172), 1.67 (d, J = 7.2 Hz, 3H, 181),
1.60 (t, J = 7.6 Hz, 3H, 82), ∼1.55 (1H, 172 concealed
by overlapping peaks). MS (ESI, positive mode): m/z
calcd for C37H40N4O5ZnH 701.2312; [M+H+] found
701.2307.
3.3.2. Pd[Chl-e]
Yield 1.9 mg, 9.4%. UV–Vis (CH2Cl2) λmax (nm)
[ϵ × 10−4 (M−1·cm−1)]: 403 (5.14), 486 (0.35), 582
(0.62), 623 (3.22). 1H NMR (400 MHz, CDCl3, δ in
ppm): 9.57 (s, 1H, 5/10), 9.56 (s, 1H, 5/10), 8.62
130 Simon Larsen et al.
Table 2. CAMY-B3LYP-D3/STO-TZ2P TDDFT results, including transition energies (E) and wavelengths
(λ), oscillator strengths ( f ), MO compositions, and symmetries
Molecule Peak E (eV) λ (nm) f MO composition State symmetry
From To Weight (%)
Zn[Chl] Q 2.12 584.6 0.45 HOMO LUMO 92.6 B
HOMO-1 LUMO+1 6.3 B
Soret 3.04 408.4 1.80 HOMO LUMO+1 62.3 A
HOMO-1 LUMO 35.8 A
3.33 372.3 1.23 HOMO-1 LUMO+1 91.4 B
HOMO LUMO 6.4 B
Pd[Chl] Q 2.18 568.4 0.48 HOMO LUMO 94.3 B
HOMO-1 LUMO+1 4.5 B
Soret 3.11 398.7 1.60 HOMO-1 LUMO 59.8 A
HOMO LUMO+1 38.2 A
3.47 356.9 1.10 HOMO-1 LUMO+1 92.5 B
HOMO LUMO 4.5 B
Pt[Chl] Q 2.23 556.1 0.50 HOMO LUMO 94.8 B
HOMO-1 LUMO+1 3.9 B
Soret 3.18 390.1 1.58 HOMO LUMO+1 56.5 A
HOMO-1 LUMO 40.9 A
3.56 348.4 1.14 HOMO-1 LUMO+1 92.6 B
HOMO LUMO 3.8 B
(s, 1H, 20), 7.98 (dd, J = 17.8, 11.5 Hz, 1H, 31), 6.16
(dd, J = 17.8, 1.7 Hz, 1H, 32 trans), 6.03 (dd, J =
11.5, 1.7 Hz, 1H, 32 cis), 5.14 (d, J = 19.1 Hz, 1H,
151), 4.93 (d, J = 19.0 Hz, 1H, 151), 4.48–4.35 (m, 2H,
overlapping 17 and 18), 4.19 (s, 3H, OCH3), 3.86 (s,
3H, OCH3), 3.75 (q, J = 7.6 Hz, 2H, 81), 3.62 (s, 3H,
OCH3), 3.44 (s, 3H, 121), 3.33 (s, 3H, 21), 3.29 (s, 3H,
71), 2.58–2.46 (m, 1H, 171), 2.24–2.11 (m, 1H, 171),
2.07–1.95 (m, 1H, 172), 1.75 (d, J = 7.1 Hz, 3H, 181),
1.69 (t, J = 7.6 Hz, 3H, 82) ∼1.69 (1H, 172 concealed
by overlapping peaks). MS (APCI, positive mode):
m/z calcd for C37H40N4O5PdH 743.2055; [M + H+]
found 743.2065.
3.3.3. Pt[Chl-e]
Yield 5.8 mg, 24.7%. UV–Vis (CH2Cl2) λmax (nm)
[ϵ × 10−4 (M−1·cm−1)]: 393 (6.49), 478 (0.36), 613
(3.49). 1H NMR (400 MHz, CDCl3, δ in ppm): 9.56
(s, 1H, 5), 9.52 (s, 1H, 10), 8.70 (s, 1H, 20), 7.98 (dd,
J = 17.8, 11.5 Hz, 1H, 31), 6.14 (dd, J = 17.8, 1.7 Hz,
1H, 32 trans), 6.02 (dd, J = 11.4, 1.6 Hz, 1H, 32 cis),
5.13 (d, J = 19.1 Hz, 1H, 151), 4.93 (d, J = 19.1 Hz, 1H,
151), 4.46–4.34 (m, 2H, overlapping 17 and 18), 4.20
(s, 3H, OCH3), 3.87 (s, 3H, OCH3), 3.71 (q, J = 7.6 Hz,
2H, 81), 3.63 (s, 3H, OCH3), 3.50 (s, 3H, 121), 3.31
(s, 3H, 21), 3.24 (s, 3H, 71), 2.54 (ddd, J = 16.1, 9.0,
7.0 Hz, 1H, 171), 2.20 (ddd, J = 16.2, 7.2, 4.8 Hz,
1H, 171), 2.09–1.97 (m, 1H, 172), 1.76 (d, J = 7.1 Hz,
3H, 181), 1.68 (t, J = 7.6 Hz, 3H, 82), ∼1.71 (1H, 172
concealed by overlapping peaks). MS (APCI, posi-
tive mode): m/z calcd for C37H40N4O5PtH 832.2668;
[M+H+] found 832.2670.
3.4. Computational method
The three M[Chl] (M = Zn, Pd, Pt] complexes were
optimized with scalar-relativistic DFT calculations,
with the OLYP [20,21] functional augmented with
Grimme’s D3 [22] dispersion correction, all-electron
ZORA STO-TZ2P basis sets, fine integration grids,
Simon Larsen et al. 131
Figure 5. CAMY-B3LYP-D3/STO-TZ2P-COSMO
frontier MO energy levels along with C2 irreps (a
and b).
Figure 6. Simulated TD-CAMY-B3LYP-D3/
STO-TZ2P-COSMO optical spectra in
dichloromethane. The vertical lines repre-
sent calculated transitions which have then
been broadened with Gaussians to generate
the simulated spectra.
and tight criteria for both SCF cycles and geome-
try optimizations, as implemented in the ADF 2019
program system [25]. All the optimizations were
carried out with a C2 symmetry constraint and the
COSMO (Conductor like Screening Model) [26] solva-
tion model with dichloromethane as solvent. TDDFT
calculations were performed on the OLYP-D3 opti-
mized geometries using the CAMY-B3LYP [24] range-
separated functional (which has been extensively cal-
ibrated for calculations of porphyrin spectra [4,7,27]),
with basis set and other parameters the same as in
the ground-state calculations).
Declaration of interests
The authors do not work for, advise, own shares in,
or receive funds from any organization that could
benefit from this article, and have declared no affil-
iations other than their research organizations.
Funding
This research was supported by the Research Council
of Norway (grant no. 262229 to AG), the CNRS (grant
UMR UBCNRS 6302), and the South African National
Research Foundation (grant nos. 129270 and 132504
to JC).
Acknowledgment
The authors also warmly thank Mrs. Sandrine Pac-
quelet for technical assistance.
Supplementary data
Supporting information for this article is available on
the journal’s website under https://doi.org/10.5802/
crchim.299 or from the author.
References
[1] A. Ghosh, Angew. Chem. Int. Ed., 2021, 60, 9760-9770.
[2] M. Gouterman, G. H. Wagniére, L. C. Snyder, J. Mol. Spectrosc.,
1963, 11, 108-115.
[3] M. Gouterman, in The Porphyrins (D. Dolphin, ed.), vol. III,
Part A, Academic Press, New York, 1978, 1-165.
[4] C. C. Wamser, A. Ghosh, JACS Au, 2022, 2, 1543-1560.
[5] Y. Lin, T. Zhou, R. Bai, Y. Xie, J. Enzyme Inhib. Med., 2020, 35,
1080-1099.
[6] K. C. Tong, D. Hu, P. K. Wan, C. N. Lok, C. M. Che, Adv. Inorg.
Chem., 2020, 75, 87-119.
[7] A. B. Alemayehu, K. E. Thomas, R. F. Einrem, A. Ghosh, Acc.
Chem. Res., 2021, 54, 3095-3107.
[8] A. Ghosh, J. Conradie, J. Phys. Chem. A, 2021, 125, 9962-9968.
132 Simon Larsen et al.
[9] A. Ghosh, T. Wondimagegn, A. B. Parusel, J. Am. Chem. Soc.,
2000, 122, 5100-5104.
[10] A. Ghosh, Chem. Rev., 2017, 117, 3798-3881.
[11] A. Alemayehu, J. Conradie, A. Ghosh, Eur. J. Inorg. Chem.,
2011, 12, 1857-1864.
[12] S. Ganguly, A. Ghosh, Acc. Chem. Res., 2019, 52, 2003-2014.
[13] I. K. Thomassen, A. Ghosh, ACS Omega, 2020, 5, 9023-9030.
[14] A. J. McHugh, M. Gouterman, C. Weiss, Theor. Chim. Acta,
1972, 24, 346-370.
[15] A. Zhang, M. J. Stillman, Phys. Chem. Chem. Phys., 2018, 20,
12470-12482.
[16] E. Fujita, C. K. Chang, J. Fajer, J. Am. Chem. Soc., 1985, 107,
7665-7669.
[17] S. Licoccia, M. J. Chatfield, G. N. La Mar, K. M. Smith, K. E.
Mansfield, R. R. Anderson, J. Am. Chem. Soc., 1989, 111, 6087-
6093.
[18] A. Ghosh, J. Phys. Chem. B, 1997, 101, 3290-3297.
[19] A. B. Parusel, A. Ghosh, J. Phys. Chem. A, 2000, 104, 2504-2507.
[20] N. C. Handy, A. J. Cohen, Mol. Phys., 2001, 99, 403-412.
[21] C. Lee, W. Yang, R. G. Parr, Phys. Rev. B, 1988, 37, 785-789.
[22] S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys., 2010,
132, article no. 154104.
[23] H. Ryeng, E. Gonzalez, A. Ghosh, J. Phys. Chem. B, 2008, 112,
15158-15173.
[24] Y. Yakinaga, S. Ten-no, Chem. Phys. Lett., 2008, 462, 348-351.
[25] G. te Velde, F. M. Bickelhaupt, S. J. A. van Gisbergen, C. F.
Guerra, E. J. Baerends, J. G. Snijders, T. Ziegler, J. Comp.
Chem., 2001, 22, 931-967.
[26] A. Klamt, G. Schüürmann, J. Chem. Soc., Perkin Trans., 1993,
2, 799-805.
[27] J. Conradie, C. C. Wamser, A. Ghosh, J. Phys. Chem. A, 2021,
125, 9953-9961.


Hypsochlorins

Comptes Rendus
Chimie
Laurent Cassayre and Hervé Muhr
Special issue on hydrometallurgical processes for the integrated management of
primary and secondary resources: Foreword
Volume 27, Special Issue S4 (2024), p. 3-4
Online since: 15 May 2025
Part of Special Issue: GDR Prométhée – French Research Network on
Hydrometallurgical Processes for Primary and Secondary Resources
Guest editors: Laurent Cassayre (CNRS-Université de Toulouse, Laboratoire de Génie
Chimique, France) and Hervé Muhr (CNRS-Université de Lorraine, Laboratoire
Réactions et Génie des Procédés, France)
https://doi.org/10.5802/crchim.401
This article is licensed under the
Creative Commons Attribution 4.0 International License.
http://creativecommons.org/licenses/by/4.0/
C EN T R E
MER S ENN E
The Comptes Rendus. Chimie are a member of the
Mersenne Center for open scientific publishing
www.centre-mersenne.org — e-ISSN : 1878-1543
Comptes Rendus. Chimie
2024, Vol. 27, Special issue S4, p. 3-4
https://doi.org/10.5802/crchim.401
Foreword
GDR Prométhée – French Research Network on Hydrometallurgical
Processes for Primary and Secondary Resources
Special issue on hydrometallurgical processes for the
integrated management of primary and secondary
resources: Foreword
Laurent Cassayre and HervéMuhr
This special issue is the initiative of the Prométhée
GDR, a national research group dedicated to the
study of hydrometallurgical processes for the inte-
grated management of primary and secondary re-
sources. This GDR was created in January 2016 and
renewed in 2021, and brings together around 150 re-
search actors from 27 academic laboratories, as well
as CEA, IFPEN and BRGM teams. It contributes to
structure French research community on hydromet-
allurgical processes, for a better management of non-
energy mineral resources, from mining to recycling.
The CNRS, via its two institutes “Chemistry” and “En-
gineering”, is funding this GDR.
The community was invited to submit part of their
work for this special issue of the journal Comptes
Rendus de l’Académie des Sciences. Following a
standard review process, 13 of these articles have
been published, among which four review articles
and nine research papers. They cover and com-
bine a wide range of scientific fields, from chemi-
cal engineering, separation chemistry, electrochem-
istry, biometallurgy, physical chemistry or mechano-
chemistry, and address a various range of metal el-
ements, such as noble metals, transition metals,
lithium, rare earths, uranium and actinides. More
specifically, this special issue starts with a presen-
tation of a specific classification process for elec-
tronic wastes [1]. Then four articles are dedicated
to leaching and bioleaching processes [2–5], three
articles deal with both leaching and precipitation
operations [6–8], two focus on precipitation [9,10],
two consider chemical aspects of solvent extrac-
tion [11,12] and a last paper is dedicated to elec-
trometallurgy of noble metals in deep eutectic sol-
vents [13].
We would like to thank all authors for their impli-
cation in this Special Issue, as well as the >30 review-
ers who provided many valuable insights on these
papers.
Laurent Cassayre
Laboratoire de Génie Chimique
Toulouse
France
laurent.cassayre@ensiacet.fr
Hervé Muhr
Laboratoire Réactions et Génie des Procédés
Nancy
France
herve.muhr@univ-lorraine.fr
References
[1] N. M. Charpentier, D. Xia and J.-C. P. Gabriel, “Printed cir-
cuit board recycling: a focus on a novel, efficient and sus-
tainable process for spent critical metals recovery”, C. R.
Chim. 27 (2024), pp. 5–15.
ISSN (electronic): 1878-1543 https://comptes-rendus.academie-sciences.fr/chimie/
4 Laurent Cassayre and Hervé Muhr
[2] A. Hubau, K. Bru, S. I. Oumarou and C. Leycuras, “Lessons
learned from the upscaling of an iron bio-oxidation pro-
cess to improve uranium recovery”, C. R. Chim. 27 (2024),
pp. 17–35.
[3] C. Laskar, A. Dakkoune, C. Julcour, F. Bourgeois, B. Biscans
and L. Cassayre, “Case-based analysis of mechanically-
assisted leaching for hydrometallurgical extraction of crit-
ical metals from ores and wastes: application in chalcopy-
rite, ferronickel slag, and Ni-MH black mass”, C. R. Chim.
27 (2024), pp. 37–52.
[4] E. Régnier, A. Hubau, S. Touzé, S. Guignot, D. Meyer, O.
Diat and D. Bourgeois, “Copper leaching with aqueous
foams for the processing of electronic waste”, C. R. Chim.
27 (2024), pp. 53–61.
[5] J. Jacob, D. Pino-Herrera, C. Greffié, G. Wille and E.
Plat, “Reprocessing of waste produced during acid mine
drainage lime treatment by selective leaching”, C. R. Chim.
27 (2024), pp. 63–80.
[6] M. De Souza Buriti, P. Cézac and L. Casás, “Dissolution and
precipitation of jarosite-type compounds: state of the art
and future perspectives”, C. R. Chim. 27 (2024), pp. 81–109.
[7] C. Manfoumbi, K. Roger and M. Meireles, “Filtering the un-
filterable: tuning the mesostructure of precipitating silica
gels to improve the filterability of acidic lixiviation slur-
ries”, C. R. Chim. 27 (2024), pp. 111–122.
[8] V. Nachbaur, F. Ayadi, B. Foulon, M. Jean, V. Pralong and
S. Jouen, “A sustainable solvothermal process extracting
critical elements from Li-ion batteries”, C. R. Chim. 27
(2024), pp. 123–132.
[9] L. E. Ramirez Velazquez and H. Muhr, “Lithium recov-
ery from secondary sources: A review in battery recycling
with emphasis on chemical precipitation”, C. R. Chim. 27
(2024), pp. 133–141.
[10] J. Réaux-Durain, B. Mortada, M. Bertrand, J. Maynadié,
M. Carboni, D. Meyer and D. Bourgeois, “Back-extraction
of major actinides from organic phase through precipita-
tion”, C. R. Chim. 27 (2024), pp. 143–152.
[11] F. Giusti, E. Guerinoni, D. Lemire, M. Thimotée, G. Ar-
rachart, S. Dourdain and S. Pellet-Rostaing, “Solvent ex-
traction of uranium from an acidic medium for the front-
end of nuclear fuel cycle: from mechanisms understand-
ing to innovative process design”, C. R. Chim. 27 (2024),
pp. 153–183.
[12] A. El Maangar, J. Gramüeller, V. Huber, P. Degot, D.
Touraud, R. M. Gschwind, W. Kunz and T. Zemb,
“Solubilisation–microstructure relationship of trivalent
salts in hydrotropic ternary systems”, C. R. Chim. 27
(2024), pp. 185–202.
[13] C. Bertoloni, V. Mba Ekomo, B. Villemejeanne, C. Lemoine,
R. Duwald, E. Billy, H. Mendil-Jakani and S. Legeai, “Propy-
lene glycol-based deep eutectic solvent as an alternative
to Ethaline for electrometallurgy”, C. R. Chim. 27 (2024),
pp. 203–214.


Guest Editors

Fabrice Giusti

Elise Guerinoni

David Lemire

Marine Thimotée

Guilhem Arrachart

Sandrine Dourdain

Stéphane Pellet-Rostaing

Solvent extraction of uranium from an acidic medium for the front-end of nuclear fuel cycle: from mechanisms understanding to innovative process design

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Hypsochlorins

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Solvent extraction of uranium from an acidic medium for the front-end of nuclear fuel cycle: from mechanisms understanding to innovative process design

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