Syntheses, characterizations and crystal structures of four zinc(II) and cadmium(II) complexes constructed by ligand bearing poly-coordination atoms

Treatment of 3-(4-carboxyphenylhydrazono)pentane-2,4-dione (HL) with transition metal ions afforded four novel complexes, [Zn(L)(μ₂-OOCCH₃)(H₂O)]_n (1), [Zn(L)₂(MeOH)₄] (2), {[Cd₄(η²-L)₄(μ₂-η²-L)₄(H₂O)₄(MeOH)₂]·MeOH} (3) and [Cd(η²-L)(μ₂-η²-OOCCH₃)(H₂O)₂]_n (4). Their crystal structures have been characterized by single-crystal X-ray crystallography. In polymer 1, the acetate anions bridge the Zn(II) ions forming an infinite one-dimensional (1-D) chain with L⁻ units acting as monodentate ligands in the side chain. In mononuclear complex 2, two L⁻ ligands act as monodentate fashion to coordinate to the Zn(II) ion. In its solid-state structure, [Zn(L)₂(MeOH)₄] groups are joined together by hydrogen bonds forming a three-dimensional (3-D) supramolecular network. In tetranuclear complex 3, four Cd(II) ions are linked by four μ₂-η²-L⁻ ligands, and chelated by another four L⁻ ligands, respectively. In polymer 4, the acetate anions bridge the Cd(II) ions leading to a 1-D chain containing chelating L⁻ units in the side chain.     

Conformation-controlled assembly of coordination polymers with 1,2-bis(3-pyridylcarboxamide)benzene: Structures and properties

Self-assembly of 1,2-bis(3-pyridylcarboxylamide)benzene (H₂bpb) with sulfate salts gave rise to three new coordination polymers, [Ni₂(H₂bpb)₂(H₂O)₂(CH₃OH)₂(SO₄)₂]_n · nCH₃OH 1, [Co₂(H₂bpb)₂(CH₃OH)₂(DMF)₂(SO₄)₂]_n · 0.5nH₂O 2 (DMF = N,N′-dimethylformamide) and [Zn₂(H₂bpb)₂(CH₃OH)₂(DMF)₂(SO₄)₂]_n · 0.5nH₂O 3. They all crystallize in a monoclinic space group C2/c, with two crystallographically distinct metal nodes being surrounded by slightly distorted octahedra. There is a homologous chair-like unit with bridging ligand H₂bpb as the back and bis(monodentate) sulfate anion as the seat in their crystal structures. Through the recognition of strong π?π stacking interactions between benzene rings, those chains formed by the unlimited extension of the chair-like units stack up to produce 1-D channels along c axis where lattice molecules and terminal ligands are accommodated. Interestingly, the trans,trans,syn achiral conformation with C_s symmetry of H₂bpb which is further enforced by sulfate-bridged coordination and intramolecular hydrogen bonding in the chair-like units, controls over the assembling architectures. Further investigation on the thermal and fluorescent properties of complexes 1-3 shows that the homologous chair-like units in all complexes are stable enough until to 320 °C and that the fluorescence nature of H₂bpb is not sensitive to its conformations.     

Metallocycle and ring-opening polymerization of silver(I) complexes with 1,3-bis(4,5-dihydro-1H-imidazol-2-yl)benzene ligand

The reaction of 1,3-bis(4,5-dihydro-1H-imidazol-2-yl)benzene (bib) ligand with silver(I) nitrate in a 1:1 molar ratio generated a [2 + 2] metallocyclic complex [Ag₂(bib)₂](NO₃)₂ · 2H₂O, in which bib ligand displayed in cis configuration. When the additional competing ligands/counterions, such as oxlate salt, 1,2-diaminoethene (en), 1,3-diaminopropane (pn), and were introduced, respectively, to the above-mentioned reaction solution, ring-open polymerization of sliver(I) complexes {[Ag(bib)]NO₃ · H₂O}_n (1), {[Ag(bib)₂]X}_n ( (2), (3)), {[Ag₂(bib)₂(NO₂)](NO₂) · 19/8H₂O}_n (4) and {[Ag₂(bib)₂](V₄O₁₂)_0.5 · 3H₂O · 2MeCN}_n (5) were generated. In compounds 1, 4 and 5, bib ligand adopts trans configuration and twists around the Ag-Ag axis, giving rise to single-stranded helical structure with short adjacent Ag?Ag distances of 3.56, 3.56, 3.50 and 3.63 Å, respectively. Compounds 2 and 3 are 1D coordination polymers fusing the [2 + 2] metallocycle [Ag₂(bib)₂]²⁺, in which bib ligand exhibits in cis configuration and the metallocycles have longer Ag?Ag distances of 8.52 Å in 2 and 8.61 Å in 3 along with the strong intracyclicπ-π interactions between phenyl groups. Cis and trans configurations of bib coexist in solution and crystallize in complexes 1 and 2 in the solid state in the presence of en or pn. The solution of 1 and 2 can be converted into 3 via the addition of the bulky counter anion or into 4 through introduction of the competing ligand/conuterion .     

Copper(I) bromide complexes from 1,2-bis(diphenylphosphano) benzene and some heterocyclic thiones

The synthesis, characterization and solid state emission properties of a series of mixed-ligand copper(I)bromide complexes containing 1,2-bis(diphenylphosphano)benzene (dppbz) and some heterocyclic thiones (L) are reported. The complexes are readily synthesized by the addition of the appropriate thione to a CuBr-diphosphane adduct in acetonitrile/methanol or acetone solution. The molecular structures of [CuBr(dppbz)(py2SH)], [CuBr(dppbz)(pymtH)] and [CuBr(dppbz)(imdtH₂)] were established by single-crystal X-ray diffraction. Each of these structures features a tetrahedral copper(I) centre with two phosphorus atoms from the chelating diphos ligand, one bromine and the exocyclic sulfur atom of the heterocyclic thioamide unit. Slow decomposition of the mixed-ligand complexes via ligand dissociation occurs when their chloroform solutions are left to stand at room temperature for several weeks. On the basis of elemental analysis, NMR and IR spectra, the resulting coloured crystals are found to contain phosphane-free coordination polymers of composition [CuBr(L)]. At room temperature, some of the molecular complexes in the solid state exhibit strong emission assigned to a metal-ligand charge transfer of type Cu(I) → π*(PPh₂).     

Syntheses and characterization of copper complexes with the ligand 2-aminoethyl(2-pyridylmethyl)-1,2-ethanediamine (apme)

Copper(I)/(II) complexes with the ligand 2-aminoethyl(2-pyridylmethyl)1,2-ethanediamine (apme, abbreviated as PDT in the literature as well) were prepared and characterized. Crystal structures of the copper(I) complexes, [Cu₂(apme)₂]X₂ (1, 2; X = ClO₄, CF₃SO₃), showed that they are dinuclear, in contrast to the trigonal bipyramidal copper(II) complexes [Cu(apme)Cl]BPh₄ (3) and [Cu(apme)(DMF)](BPh₄)₂ (4). 1 and 2 could be investigated in solution by NMR spectroscopy and 3 and 4 by cyclovoltammetry. From the results of these studies it is clear that in solution equilibria between the dinuclear complexes 1/2 and another species exist, most likely the monomeric [Cu(apme)CH₃CN]⁺. Time-resolved UV/vis spectra at low temperatures allowed the spectroscopic detection of dioxygen adduct complexes as reactive intermediates during the oxidation of 1/2 with dioxygen that seem to play an important role in copper enzymes such as peptidylglycine--hydroxylating monooxygenase (PHM).     

Chair-form [Ag2(1,2-bimb)2] in silver(I) complexes containing the ditopic ligand 1,2-bis(1-imidazolylmethyl)benzene (1,2-bimb)

The ditopic ligand 1,2-bis(1-imidazolylmethyl)benzene (1,2-bimb) and its silver(I) complexes [Ag₂(1,2-bimb)₂](PF₆)₂ (1) and {[Ag₂(1,2-bimb)₂]₂(SbF₆)₄}_n (2) were prepared and their structures characterized by X-ray crystallography. Both complexes contain the chair-form unit [Ag₂(1,2-bimb)₂]²⁺ with Ag(I) linearly coordinated by N_Im (Im=1-imidazolyl) from the Im groups of two 1,2-bimb. However, the [Ag₂(1,2-bimb)₂]²⁺ units are positioned differently in forming 1D infinite chains through weak argentophilic interactions: linear chains in 1 with the units oriented in same direction are formed via Ag?π interactions, while polymeric chains constructed via Ag?Ag interactions in 2 are observed with the units arranged in alternate directions. Differences in supramolecular structures may be a result of different size of the anions.     

Novel cup-like helical coordination polymers: synthesis, crystal structures and thermal properties

By the design of ligand 1,1^′-(1,5-pentamethylene)bis-1H-benzimidazole (pbbm), we have synthesized polymers {[Co(NO₃)(pbbm)₂]NO₃ · 1/2H₂O}_n (1), {[CdCl(pbbm)₂]Cl · CH₃OH}_n (2) and {[Cu(Ac)₂(pbbm)] · CH₃OH}_n (3), and characterized their structures by single crystal X-ray diffraction as well as thermoanalysis. In polymers 1 and 2, one of the anions coordinates to the central ion, the other is located in the environment. Two pbbm ligands coordinate simultaneously to two metal centers generating one-dimensional cup-like helical chains. To our best knowledge, this cup-like structure has never been observed in the reported polymers. In polymer 3, each Cu atom is five-coordinate by two nitrogen atoms from two pbbm ligands, and three oxygen atoms from one monodentate acetate anion and one chelating acetate anion leading to one-dimensional wave-like linear chain. In addition, the DTA and TG results of the three polymers are in agreement with the crystal structures.     

Crystal structure, thermal stability and theoretical investigation on four 1,3-bis(1,2,4-triazol-1-yl)propane-based copper(II) complexes

Self-assembly of flexible 1,3-bis(1,2,4-triazol-1-yl)propane (btp), inorganic Cu(II) salt and rigid benzene-based carboxylate coligand generates four complexes, {[Cu(btp)₂(CH₃OH)(H₂O)]·H₂O·2ClO₄}_n (1), {[Cu(btp)(Hbtc)₂]·0.5H₂O}_n (2), [Cu(btp)₂(H₃btea)₂]_n (3), and [Cu(btp)(nb)₂] (4) (H₃btc = 1,3,5-benzenetricarboxylic acid, H₄btea = 1,2,4,5-benzenetetracarboxylic acid, Hnb = p-nitrobenzoic acid), which are fully structural characterized by single-crystal X-ray crystallography, elemental analysis, IR, and TG-DTA techniques. Structural determinations reveal that the polymeric two-dimensional (2D) Cu-btp grid-like layer for 1, 1D linear single- and double-stranded chains for 2 and 3, as well as the discrete binuclear structure for 4, are jointly directed by the coordination polyhedrons of the Cu(II) ion and the exo-bidentate bridging btp core ligand with various conformations. The theoretical calculations suggest that the trans-trans btp is the most stable conformation, and the metal binding site is collectively determined by the electron density of N donors and the spatial orientation of the btp ligand. Unexpectedly, the polycarboxylate anions in 1-4 can only act as terminal coligands not popular bridging connectors. The thermal stability of the resulting complexes is also compared.     

Structural aspects of some 2:1 dipyridylamine complexes of some copper(II) salts: An interesting new polymorph of the binuclear carbonate/perchlorate tetrahydrate adduct

Recent work has described the structural characterization of the complexes :dpyam:H₂O (1:4:4), X′ = ClO₄, BF₄, ‘dpyam’ = dipyridylamine, as a pair of triclinic Z = 1 isomorphs, the cations being modelled in terms of pairs of copper atoms bridged by a carbonate ion disordered about a crystallographic inversion centre. This work has been revisited in the course of describing a new polymorph of the perchlorate in a triclinic cell of twice the size, in which the carbonate unit, now non-disordered, bridges a pair of crystallographically independent copper atoms which display distinctly different coordination environments, one close to the square-pyramidal norm, the other not. Studies of adducts of the form [(dpyam)₂CuX]X′(·nH₂O) are also recorded. The X/X′ = propionate/iodide adduct is found to be isomorphous with its acetate/BF₄ but, interestingly, not its propionate/Cl counterpart. ‘Low’-temperature redeterminations of the NCO/Cl · 4H₂O and nitrite/ClO₄ adducts are also recorded, enabling definition of the hydrogen-bonding scheme in the former.     

Structural and biochemical studies of GH family 12 cellulases: improved thermal stability, and ligand complexes

In this review we will describe how we have gathered structural and biochemical information from several homologous cellulases from one class of glycoside hydrolases (GH family 12), and used this information within the framework of a protein-engineering program for the design of new variants of these enzymes. These variants have been characterized to identify some of the positions and the types of mutations in the enzymes that are responsible for some of the biochemical differences in thermal stability and activity between the homologous enzymes. In this process we have solved the three-dimensional structure of four of these homologous GH 12 cellulases: Three fungal enzymes, Humicola grisea Cel12A, Hypocrea jecorina Cel12A and Hypocrea schweinitzii Cel12A, and one bacterial, Streptomyces sp. 11AG8 Cel12A. We have also determined the three-dimensional structures of the two most stable H. jecorina Cel12A variants. In addition, four ligand-complex structures of the wild-type H. grisea Cel12A enzyme have been solved and have made it possible to characterize some of the interactions between substrate and enzyme. The structural and biochemical studies of these related GH 12 enzymes, and their variants, have provided insight on how specific residues contribute to protein thermal stability and enzyme activity. This knowledge can serve as a structural toolbox for the design of Cel12A enzymes with specific properties and features suited to existing or new applications.     

Structural variations and spectroscopic properties of copper(I) complexes with bis(schiff base) ligands

Six copper(I) complexes {[Cu₂(L1)(PPh₃)₂I₂] · 2CH₂Cl₂}_n (1), {[Cu₂(L2)(PPh₃)₂]BF₄}_n (2), [Cu₂(L3)(PPh₃)₄I₂] · 2CH₂Cl₂ (3), [Cu₂(L4)(PPh₃)₄I₂] (4), [Cu₂(L5)(PPh₃)₂I₂] (5) and [Cu₂(L6)(PPh₃)₂I₂] (6) have been prepared by reactions of bis(schiff base) ligands: pyridine-4-carbaldehyde azine (L1), 1,2-bis(4′-pyridylmethyleneamino)ethane (L2), pyridine-3-carbaldehyde azine (L3), 1,2-bis(3′-pyridylmethyleneamino)ethane (L4), pyridine-2-carbaldehyde azine (L5), 1,2-bis(2′-pyridylmethyleneamino)ethane (L6) with PPh₃ and copper(I) salt, respectively. Ligand L1 or L2 links (PPh₃)₂Cu₂(μ-I)₂ units to form an infinite coordination polymer chain. Ligand 3 or 4 acts as a monodentate ligand to coordinate two copper(I) atoms yielding a dimer. Ligand 5 or 6 chelates two copper(I) atoms using pyridyl nitrogen and imine nitrogen to form a dimer. Complexes 1-4 exhibit photoluminescence in the solid state at room temperature. The emission has been attributed to be intraligand π-π* transition mixed with MLCT characters.     

Syntheses, structures and photoluminescent properties of two zinc(II) coordination polymers based on aromatic polycarboxylate and 1,4-bis(imidazol-1-ylmethyl)benzene

Hydrothermal reaction of Zn(NO₃)₂·6H₂O with benzene-1,2,3-tricarboxylic acid (H₃BTC) or 5-bromoisophthalic acid (H₂BIPA) in the presence of 1,4-bis(imidazol-1-ylmethyl)benzene (bix) produced two novel coordination polymers [Zn₂(OH)(BTC) (bix)]·H₂O (1) and Zn(BIPA)(bix) (2), which were characterized by single-crystal X-ray diffraction, elemental analysis, IR and thermoanalysis. Complex 1 is a novel example of the 2D (3,4)-connected nets with (4²·6)(4²·6³·8) topology. In 2, the BIPA and bix ligands linked the Zn(II) atoms into a deeply corrugated 2D sheet. The corrugated 2D sheets polycatenate each other in a parallel manner yielding a rare 2D → 3D parallel polycatenation net. Thermal and luminescent properties of two complexes have also been investigated.     

Trans-1,2-bis(diphenylphosphino)ethene as bridging ligand in thione-S-ligated dimeric copper(I) chloride complexes

Several mixed-ligand complexes have been prepared by treatment of copper(I) chloride with equimolar amounts of trans-1,2-bis(diphenylphosphino)ethene (trans-dppen) in acetonitrile followed by the addition of a methanolic solution of one equivalent of a heterocyclic thione (L). The novel complex compounds have been characterized by single-crystal X-ray diffraction, ¹H NMR and IR spectroscopy as well as by elemental analyses and melting points. The X-ray structures of three examples confirm that the compounds are homobimetallic dimers of type [CuCl(μ₂-trans-dppen)(L)]₂ containing two tetrahedral coordination units joined by two trans-dppen bridges.     

Transition metal complexes with pyrazole based ligands, part 18: new binuclear Cu(I), Cu(II) and Co(II) complexes with 3,5-dimethyl-1-thiocarboxamide pyrazole: synthesis, structural and magnetic studies

Three new binuclear metal complexes of the formulas (L = 3,5-dimethyl-1-thiocarboxamide pyrazole) have been synthesized and characterized by chemical analysis, FT-IR spectroscopy, solution conductivity, solid state magnetic measurements and X-ray single crystal and variable temperature powder diffraction. Complex 1 forms doubly chloro-bridged dimers, with Cu(II) in distorted trigonal bipyramidal coordination with the apical positions occupied by chlorine atoms. Magnetic measurements indicate an antiferromagnetic interaction between the Cu(II) centres in the dimer, with the singlet-triplet exchange parameter of J = −19.40 cm⁻¹. Complex 2 forms doubly sulfur-bridged dimers, with Cu(I) in distorted tetrahedral coordination with apical positions occupied by bromine atoms. Complex 3 is a cobalt analogue of 1. It contains dinuclear units formed by five-coordinate high-spin Co(II) in a distorted trigonal bipyramidal environment. The magnetisation of 3 shows no significant departure from Curie-Weiss behaviour between room temperature and 5 K. All crystal structures are stabilized by two-dimensional hydrogen bonding networks between the carboxamide nitrogen donors and the terminal halide acceptors.     

Synthesis, structures and spectroscopic properties of new 1,2-bis[2-(4-methyl-7-acetylamino-1,8-naphthyridine)]ethylene ligand and its binuclear copper(I) complexes

The synthesis, characterization, spectroscopic properties of a new ligand 1,2-bis[2-(4-methyl-7-acetylamino-1,8-naphthyridine)]ethylene (L) and its two binuclear Cu(I) complexes containing triphenylphosphine (PPh₃) or bis(diphenylphosphino)methane (dppm), [Cu₂(L)(PPh₃)₄](BF₄)₂·2CH₂Cl₂ (1·2CH₂Cl₂) and [Cu₂(L)(dppm)₂](BF₄)₂·4H₂O (2·4H₂O) are reported. The structural investigation of these compounds based on X-ray crystal analysis shows that the copper(I) centers adopt different coordination geometries, O(N)CuP₂⁺ and NCuP₂⁺ for complexes 1 and 2, respectively. Upon irradiation of a degassed organic solution of L at 365 nm, photoinduced isomerization reaction and an intramolecular proton transfer of ligand L were detailed studied by absorption spectral changes. A spectroscopic investigation involving time-dependent density functional theory calculations allows assignment of the excited states that relate to emission and transient absorption spectra. The observed lower-energy absorption bands appearing in the region of 413 and 418 nm for 1 and 2 in dichloromethane are assigned to ligand-to-ligand charge transfer (LLCT, phosphine → napy) transition in nature. Compared with well-structured solid-state emission originating from ππ^∗ transition of ligand L, complexes 1 and 2 exhibit intense room-temperature solid-state emissions with λ_max at 586 and 620 nm, respectively. The energy and the shape of the emission bands are clearly different from that of the ligand, indicating the emissions come from different excited states.     

Nickel(II)-, cobalt(II)-, copper(II)-, and zinc(II)-phthalate and 1-methylimidazole coordination compounds: synthesis, crystal structures and magnetic properties

Three new coordination polymers [M(Pht)(1-MeIm)₂]_n (where M=Cu (1), Zn (2), Co (3); Pht²⁻=dianion of o-phthalic acid; 1-MeIm=1-methylimidazole) and two compounds [M(1-MeIm)₆](HPht)₂ · 2H₂O (M=Co (4), Ni (5)) have been synthesized and characterized by X-ray crystallography. The structures of 1-3 (2 is isostructural to 3) consist of [M(1-MeIm)₂] building units connected by 1,6-bridging phthalate ions to form infinite chains. In complex 1, each copper(II) center adopts a square coordination mode of N₂O₂ type by two O atoms from different phthalate ions and two N atoms of 1-MeIm, whereas in 3 two independent metal atoms are tetrahedrally (N₂O₂) coordinated to a pair of Pht ligands and a pair of 1-MeIm molecules. There are only van der Waals interactions between the chains in 1, while the three-dimensional network in 3 is assembled by C-H?O contacts. In contrast to polymers 1-3 the structures of 4 and 5 (complexes are also isostructural) are made up of the [M(1-MeIm)₆]²⁺ cation, two hydrogen phthalate anions (HPht⁻) and two H₂O solvate molecules. The coordination around each metal(II) atom is octahedral with six nitrogen atoms of 1-MeIm. Extended hydrogen bonding networks embracing the solvate water molecules and a phthalate residue as well as the weak C-H?O interactions stabilize the three-dimensional structures. Magnetic studies clearly show that the magnetic ions do not interact with each other. Furthermore, in compound 4 we have another example of a highly anisotropic Co²⁺ ion with a rhombic g-tensor and large zero-field-splitting. The complexes were also characterized by IR and ¹H NMR spectroscopy, thermogravimetric analysis, and all data are discussed in the terms of known structures.     

Syntheses, structures and photoluminescence properties of cadmium(II) and zinc(II) complexes with pyridinylcarboxamide-containing ligand

Four new coordination complexes [Cd(DPBA-3)₂(H₂O)₂](ClO₄)₂·2H₂O (1), [Cd(DPBA-3)(DMF)(NO₃)₂]·DMF (2), [Cd₃(DPBA-3)₂(SCN)₆]·2DMF·4H₂O (3) and [Zn(DPBA-3)(SCN)₂] (4) [DPBA-3 = N,N′-di(pyridin-3-yl)pyridine-3,5-dicarboxamide] have been synthesized and characterized by elemental analysis, IR and single crystal X-ray diffraction. Complexes 1, 3 and 4 exhibit three different types of one-dimensional (1D) chain structures constructed by the metal ions and DPBA-3 ligands, and the Cd(II)-DPBA-3 1D chains in 3 are further linked by bridging SCN⁻ ligands to afford a three-dimensional (3D) framework. Complex 2 possesses a (6,3) two-dimensional (2D) layer structure. In 1-4, the hydrogen bonds involving the amide groups play important role to stabilize the resultant frameworks. The photoluminescence properties of the DPBA-3 and the complexes were studied in the solid state at room temperature.     

Synthesis, chemical- and electrochemical properties of ruthenium(II) complexes bearing 2,6-bis(2-naphthyridyl)pyridine

Ruthenium complexes with a terpyridine-analogous ligand, 2,6-bis(2-naphthyridyl)pyridine (bnp), have been synthesized and their chemical and electrochemical properties investigated. The structures of [Ru(bnp)(tpy)](PF₆)₂ (1) and [Ru(bnp)₂](PF₆)₂ (2) were determined by the X-ray structure analysis. The bnp localized redox potentials of 1 and 2 showed significant positive shift by 260-290 mV relative to the analogous Ru-terpyridine complexes.     

Synthesis, structural investigation and thermal stability of aqua magnesium(II) phthalocyanine adducts with 2-methoxyethylamine

Three new aqua magnesium phthalocyaninato complexes with 2-methoxyethylamine (MEA) in crystalline form have been obtained. The composition of the complexes depends on the crystallisation temperature. (MgPcH₂O)₂ · MEA (I) and (MgPcH₂O)₂ · 2MEA (II) were formed at about 170 °C and 80 °C, respectively, while room temperature (MgPcH₂O)₂ · 3MEA (III) was obtained. In all crystals the Mg atom is 4+1 coordinated, equatorially by four N-isoindole atoms of Pc ligand and axially by O atom of water molecule. The MgPc moiety is non-planar, the Mg(II) deviates by ∼0.5 Å from the N₄-isoindole plane towards the oxygen atom of water molecule. The MEA molecules in the crystals interact via hydrogen bonds with coordinated water molecules of MgPcH₂O. The arrangement of MgPcH₂O and 2-methoxyethylamine molecules is determined by O-H?N and O-H?O hydrogen bonds and by π-π interactions. The thermogravimetric analyses show characteristic steeps responsible for the loss of MEA molecules (at lower temperature) and water (at higher temperature) and finally all the complexes transform into β-MgPc. From among the complexes only complex II exhibits an intense near-IR absorption band in the solid-state, while spectra in MEA solution are identical for all the complexes.