O-donor Ligands Research Articles

Dual-emitting Mn(II) and Zn(II) halide complexes with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as ligand

The H-phosphinate 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) acts as O-donor ligand towards manganese(II) and zinc(II) halides, with the formation of tetrahedral complexes having general formula [MX2(DOPO)2] (M = Mn, X = Cl, Br, I; M = Zn, X = Br). The structure of [ZnBr2(DOPO)2] was ascertained by single-crystal X-ray diffraction. All the compounds showed appreciable photoluminescence at the solid state, with an emission band in the red region of the spectrum attributed to radiative decay from triplet states of the coordinated DOPO ligands. Such an emission is superimposed to the 4T1(4G)→6A1(6S) transition around 530–540 nm in the case of the Mn(II) derivatives and to a fluorescent band centred at 380 nm for [ZnBr2(DOPO)2]. Excitation wavelength-dependent emission was observed for [MnCl2(DOPO)2] and [MnBr2(DOPO)2]. The absorption and emission features of the coordinated DOPO ligands were rationalized by means of TD-DFT calculations.

Coordination-Delayed-Hydrolysis Method for the Synthesis and Structural Modulation of Titanium-Oxo Clusters.

ConspectusAtomically precise titanium-oxo clusters (TOCs) are the structure and reactivity model compounds of technically important TiO2 materials, which could help build structure-property relationships and achieve property modulation at the molecular level. However, the traditional formation of TOCs has relied on the poorly controllable hydrolysis of titanium alkoxide in the solvent for a long time, limiting the development of TOC structural chemistry to a great extent. In addition, easily hydrolyzable alkoxy groups would be still coordinated on the surface of the TOCs generated by this method, making the clusters sensitive and unstable to the moisture. To achieve controllable preparation of TOCs, we believe it is crucial to attenuate the hydrolysis of titanium ions in the formation process of a cluster. To this end, we have recently applied an effective coordination-delayed-hydrolysis (CDH) strategy for TOC synthesis, which provides powerful tools for tuning their structures.In this Account, at the beginning, a brief introduction to the coordination-delayed-hydrolysis strategy is supplied, and its predominant features for constructing novel TOCs are highlighted. In subsequent sections, we discuss how the applied chelating organic/inorganic ligands (named hydrolysis delayed ligands) influence the hydrolysis process of Ti4+ ions to form a large family of TOCs with various nuclearities and core structures. Various hydrolysis delayed ligands have been explored, ranging from common O-donor ligands (carboxylate, phenol, or sulfate) to rarely used N-donor ligands (pyrazole) or bifunctional O/N-donor ones (quinoline, oxime, or alkanolamine). Breakthroughs in the symmetry, configuration, and cluster nuclei of TOCs have been accordingly achieved. Then, we show that this CDH method can be used to tune the surface structure of TOCs by modifying functional organic ligands. As a result, the physicochemical properties of TOCs, especially optical band gaps, can be optimized, and their stability under ambient conditions is significantly improved. In addition, we illustrate that the reversible bonds between hydrolysis delayed ligands and Ti ions further allows us to introduce active heterometal ions or clusters upon or inside the Ti-O cores to prepare heterometallic TOCs with unprecedented structures and properties. In particular, noble metal (Ag ions or clusters) has been incorporated into Ti-O clusters for the first time. As a summary, the coordination-delayed-hydrolysis strategy has realized the controllable hydrolysis of Ti4+ ions to some extent, breaking through the limitations of traditional synthesis methods and producing fruitful results in the field of titanium-oxo clusters. It is believed that this CDH method would also be effective for synthesizing oxo clusters of other easily hydrolyzed metal ions (Al3+, Sn4+, In3+, etc.) to afford significant contribution for the cluster community.

Dual-Ligand-Oriented Design of Noncentrosymmetric Complexes with Nonlinear-Optical Activity.

When the N- and O-donor ligands are combined as coligands, two noncentrosymmetric (NCS) complexes of [Ni(p-bdc)(tipa)(H2O)2]2·H2O (1) and Ni(npdc)(tipa)H2O (2) [tipa = tris[4-(1H-imidazol-1-yl)phenyl]amine, p-H2bdc = 1,4-benzenedicarboxylic acid, and H2npdc = 2,6-naphthalenedicarboxylic acid] were achieved under solvothermal conditions. For both structures, N-donor ligands are responsible for the generation of a layered structure, while the O-donor ligands are hung on the layers and are responsible for enhancing the polarity, giving rise to the NCS structures. Because of the different connection modes between the metal centers and different carboxylate ligands (p-bdc2- in 1 and npdc2- in 2), 1 and 2 show some structural differences. The p-bdc2- ligands in 1 are suspended on the upper and lower sides of the [Ni(tipa)]n layers, while all of the npdc2- ligands in 2 hang on one side of the [Ni(tipa)]n layers and point in the same direction, which makes the two NCS complexes show phase-matchable behavior with different second-harmonic-generation (SHG) responses of about 0.9 and 1.5 times that of KH2PO4 (KDP), respectively. Theoretical studies reveal that charge transfers between Ni2+ and carboxylate ligands make the dominant contribution to the optical properties. It is expected that a dual-ligand strategy may guide the design of novel superior-performing NCS complexes.

Ammonia for post-healing of formamidinium-based Perovskite films

Solvents employed for perovskite film fabrication not only play important roles in dissolving the precursors but also participate in crystallization process. High boiling point aprotic solvents with O-donor ligands have been extensively studied, but the formation of a highly uniform halide perovskite film still requires the participation of additives or an additional step to accelerate the nucleation rate. The volatile aliphatic methylamine with both coordinating ligands and hydrogen protons as solvent or post-healing gas facilitates the process of methylamine-based perovskite films with high crystallinity, few defects, and easy large-scale fabrication as well. However, the attempt in formamidinium-containing perovskites is challenged heretofore. Here, we reveal that the degradation of formamidinium-containing perovskites in aliphatic amines environment results from the transimination reaction of formamidinium cation and aliphatic amines along with the formation of ammonia. Based on this mechanism, ammonia is selected as a post-healing gas for a highly uniform, compact formamidinium-based perovskite films. In particular, low temperature is proved to be crucial to enable formamidinium-based perovskite materials to absorb enough ammonia molecules and form a liquid intermediate state which is the key to eliminating voids in raw films. As a result, the champion perovskite solar cell based on ammonia post-healing achieves a power conversion efficiency of 23.21% with excellent reproducibility. Especially the module power conversion efficiency with 14 cm2 active area is over 20%. This ammonia post-healing treatment potentially makes it easier to upscale fabrication of highly efficient formamidinium-based devices.

Structural and Bonding Analysis in Monomeric Actinide(IV) Oxalate from Th(IV) to Pu(IV): Comparison with the An(IV) Nitrate Series.

Single-crystal X-ray diffraction (SC-XRD) structures and Raman spectra of a series of new isomorphous molecular An(IV)-oxalate compounds (Th, U, Np, and Pu) are reported. These complexes are crystallized with cobalt(III) hexamine ([Co(NH3)6]3+) as the counter cations, [Co(NH3)6]2[An(C2O4)5]·4H2O, revealing five bidentate nonbridging oxalate ligands in the first coordination sphere (CN = 10). The nonbridging oxalate is rather uncommon for An(IV)-oxalate systems, which are widely characterized as polymeric compounds. Density functional theory (DFT) calculations were performed to examine the bonding between An(IV) cations and oxalate ligands. For comparison, we also report results obtained for the An(IV)-hexanitrate series, [(C2H5)4N]2[An(NO3)6] (with An = Th, U, Np, Pu, and Ce), which consists of O-donor ligands as well but with a larger coordination number (CN = 12). The bonding analysis confirms that the actinide-oxygen bond is predominantly ionic with a minor increase in covalency from Th to U and slight variations from U to Pu. Further comparison showed that the charge transfer increases slightly when increasing the number of anions in the coordination sphere (C2O42-: CN = 10; NO3-: CN = 12), but covalent effects as indicated by the amount of internuclear electron density accumulation are small and similar for oxalate and nitrate.

Hydrophilic platinum(II) complexes containing 5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine: Spectroscopic and in vitro cytotoxic characterization

Mononuclear platinum(II) complexes with 5,7-methyl-1,2,4-triazolo[1,5-a]pyrimidine (dmtp) of the general formula cis-[Pt(X)2(dmtp)2], where X - acetate (1), trichloroacetate (2), trifluoroacetate (3), nitrate (4) have been synthesized and characterized by multinuclear magnetic resonance (1H, 13C, 15N, 195Pt) and infrared spectroscopy methods. Spectroscopic parameters indicated the presence of the PtO2N2 chromophore system with two monodentate N(3)-bonded 5,7-methyl-1,2,4-triazolo[1,5-a]pyrimidines, and two monodentate O-donor ligands (carboxylate or nitrate).A cytotoxicity assay of hydrophilic platinum(II) complexes (1–4) against three human tumour cell lines A549 (non-small cell lung carcinoma), T47D (breast cancer), HT-29 (colon adenocarcinoma), and normal murine embryonic fibroblast cells (BALB/3T3) was performed.Considering the cytotoxic parameters of the studied complexes, the best in vitro results against the human breast tumour cells (T47D) were found for cis-[Pt(OOCCCl3)2(dmtp)2] although all the tested complexes (except complex (4)) exhibited moderate in vitro activity.

Genuine Pores in a Stable Zinc Phosphite for High H2 Adsorption and CO2 Capture.

An uncommon example of stable mixed-ligand zinc phosphite with genuine pores has been synthesized by using zinc metal, inorganic phosphite acid, thio-functionalized O-donor (2,5-thiophenedicarboxylate, TPDC), and tetradentate N-donor [1,2,4,5-tetrakis(imidazol-1-ylmethyl)benzene, TIMB] units assembled into one crystalline structure according to a hydro(solvo)thermal method. This is a very rare case of a metal phosphite incorporating both N- and O-donor ligands. The tetradentate TIMB linker bound to zinc atoms of the isolated zincophosphite hexamers to form a 3D open-framework structure by crosslinking structural components of 1D chains and 2D layers. Here, the TPDC ligand acts as a monodentate binding model to functionalize its porous structure with the uncoordinated S atom and COO- group. Interestingly, this compound demonstrates the highest H2 storage capacity among organic-inorganic hybrid metal phosphates (and phosphites), and a good CO2 capture at 298 K compared with the majority of crystalline materials. The possible adsorption sites and selectivity for CO2 over H2 , N2 , and CO at 298 K were calculated by using density functional theory (DFT), the ideal adsorption solution theory (IAST), and fitting experimental pure-component adsorption data.

Rhenium Tris(pyrazolyl)borate Complexes with O-Donor Ligands: Synthesis and Structures

Rhenium Tris(pyrazolyl)borate Complexes with O-Donor Ligands: Synthesis and Structures

Silver(I) and Gold(I) Monothiocarbonate Complexes: Synthesis, Structure, Luminescence

The monothiocarbonate ligand, [S(O)COR]−, is unusual and rare regarding its use in the formation of coordination compounds. Here, we report the synthesis and structures of the silver(I) and gold(I) monothiocarbonate complexes, [{Ag4(SC(O)OiPr)2(2,2′-bpy)4}(PF6)2]n (1) and [Au2{S(O)COiPr}2(dppe)]n (2), respectively. Both complexes are coordination polymers, with 1 being cationic and 2 neutral. The uniqueness of the ligand is that it is monoanionic and contains both a ‘hard’ O-donor ligand and a ‘soft’ S-donor ligand in a O-C-S manifold with, in principle, electron delocalization across the three atoms. However, for both complexes 1 and 2, it was found that the binding occurred exclusively through the S-donor atom, while the C=O portion remained dangling and was not involved in bonding. This bonding mode departs significantly from the symmetrical S-C-S type ligand such as dithiocarbamates. The structures were analysed and confirmed by NMR and X-ray crystallography.

A Novel Method for Rapid Mineralization of Azithromycin Via Manganese Catalysts Modified with O-Donor Ligands in Hydrogen Peroxide Oxidation Process

A Novel Method for Rapid Mineralization of Azithromycin Via Manganese Catalysts Modified with O-Donor Ligands in Hydrogen Peroxide Oxidation Process

On the importance of π-stacking interactions in the complexes of copper and zinc bearing pyridine-2,6-dicarboxylic acid N-oxide and N-donor auxiliary ligands

Using N- and O-donor ligands in a mixed-ligand system, three new coordination complexes have been X-ray characterized, exhibiting strong π–π stacking interactions.

Theoretical Insights into Transplutonium Element Separation with Electronically Modulated Phenanthroline-Derived Bis-Triazine Ligands.

In the process of spent fuel reprocessing, it is highly difficult to extract transplutonium elements from adjacent actinides. A deep understanding of the electronic structure of transplutonium complexes is essential for development of steady ligands for in-group separation of transplutonium actinides. In this work, we have systematically explored the potential in-group separation ability of transplutonium elements of typical quadridentate N-donor ligands (phenanthroline-derived bis-triazine, BTPhen derivatives) through quasi-relativistic density functional theory (DFT). Our calculations demonstrate that ligands with electron-donating groups have stronger coordination abilities, and the substitutions of Br and phenol at the 4-position of the 1,10-phenanthroline have a higher effect on the ligand than those at the 5-position. Bonding analysis indicates that the covalent interaction of An3+ complexes becomes stronger from Am to Cf apart from Cm, which is because the energy of the 5f orbital gradually decreases and becomes energy-degenerate with the 2p orbitals of ligands. The most negative values of binding energies indicate the higher stability of Cf3+ complexes, in line with the larger covalency in the Cf-L bonds compared with An-L (An = Am, Cm, Bk). In addition, electron-donating group phenol can enhance the covalent interaction between ligands and heavy actinides. Consequently, the extraction ability of ligands with electron-donating substituents for heavy actinides is generally stronger than other ligands. Nevertheless, these ligands exhibit diverse separation abilities to in-group actinide recovery. Therefore, the enhancement of covalency does not necessarily lead to the improvement of separation ability, which may be caused by different extraction abilities. Compared with the tetradentate N, O-donor ligands (2,9-diamide-1,10-phenanthrolinel, DAPhen derivatives), species with BTPhen ligands display stronger covalent interaction and higher extraction capacity. In terms of in-group separation ability, the BTPhen ligands seem to have advantages in separation of californium from curium, while the DAPhen ligands possess stronger abilities to separate americium from curium. These results may afford some afflatus for the development of effective agents for in-group separation of transplutonium elements.

A pillared metal-organic framework with rich π-electron linkers as a novel fluorescence probe for the highly selective and sensitive detection of nitroaromatics

Fast and selective recognition of nitro explosives (NEs) is an emerging issue of interest. Among different detection systems, pillared metal-organic frameworks (MOFs) demonstrated high applicability in the detection of NEs. A novel pillar-layered MOF, specifically {[Zn2(2,6-NDC)2(dabco)].7DMF·3H2O} (TMU-14) were synthesized by solvothermal reaction of Zn(II) nitrate hexahydrate, 2,6-naphthalenedicarboxylic acid (2,6-NDC) as the O-donor ligand and 1,4-diazabicyclo[2.2.2]octane (dabco) as the N-donor ligand. This MOF was characterized through Single Crystal X-ray crystallography. This study demonstrated that TMU-14 with a 3D layered structure and a suitable pore window of 10.933 A˚ was an efficient luminescent sensory material through host-guest complexation with good stability and recyclability for the detection of NEs with high quantum yield.

Structure and reversible crystal-to-crystal transformations of a zinc(II) coordination polymer constructed from an imide-based dicarboxylic acid

An imide-based O-donor ligand, 4-carboxyphenyl-1,3-dioxoisoindoline-5-carboxylic acid (H2In-4-ba), and one Zn(II) coordination polymer, [Zn(In-4-ba)(py)2]n (1, py ​= ​pyridine), have been synthesized. Single-crystal X-ray diffraction indicates that 1 has a quasi-31 helical chain structure, which shows one-dimensional to two-dimensional (1D → 2D) extension to be a homochiral layer of consecutively interweaving poly-helices with the same helicity. Coexistence of such homochiral layers in opposite chirality makes individual crystal of 1 to be in a racemic manner. Thermogravimetric (TG) analysis indicated that 1 shows high thermal stability approaching 440 ​°C. Thermal activation of 1 gives a desolvated phase, [Zn(In-4-ba)]n (1′), as supported by TG trace. Of particular note, reversible crystal-to-crystal transformations between solvated 1 and desolvated 1′ have been achieved upon decoordination and recoordination of the py ligands, as evidenced by XRPD patterns, IR spectra, and TG diagrams. The photoluminescence properties of as-synthesized 1, desolvated 1′, and resolvated 1′/py have also been studied. All of them exhibit an emission band centered at 486, 492, and 486 ​nm, respectively, which is originated from the ligand-centered charge transfer. Further, the emission intensity of 1′ is weaker than that of 1 and 1′/py, implying the influence of coordinated py ligands and/or structure regulation on photoluminescence.

Syntheses, Structures and Magnetic Properties of Cobalt(II) Coordination Polymers Based on Semi-Rigid Polycarboxylic Acid Ligand

Herein, two new Co(II) CPs, {[Co(H3L)(bpa)]·H2O}n (1) and {[Co2(H3L)2(phen)2(H2O)2]·3H2O}n (2) were hydrothermally obtained based on O-donor semi-rigid polycarboxylic acid ligand H5L (5,5’-((5-carboxy-1,3-phenylene)bis(oxy))diisophthalic acid) and N-donor coligands, such as bpa (1,2-bis(4-pyridyl)ethane), phen (1,10-phenanthroline hydrate). Both of them were studied by single crystal X-ray diffraction analysis, thermogravimetric analysis, infrared spectra, powder X-ray diffraction and variable-temperature magnetic susceptibilities. CP 1 features a one-dimensional chain, further stacked to a two-dimensional layer and three-dimensional structure through π···π stacking interactions and hydrogen bonds. CP 2 displays two-dimensional layers, which further extended into three-dimensional frameworks through C−H···π interactions and hydrogen bonds. In addition, variable-temperature magnetic susceptibility data were investigated, indicating that the CPs 1 and 2 exhibited antiferromagnetic interactions.

Tin(IV) fluoride complexes with neutral phosphine coordination and comparisons with hard N- and O-donor ligands.

The reactions of trans-[SnF4(PMe3)2] with one, two or three equivalents of Me3SiO3SCF3 (TMSOTF), respectively, in anhydrous CH2Cl2 form six-coordinate [SnF4-n(PMe3)2(OTf)n] (n = 1-3), which have been characterised by microanalysis, IR and multinuclear NMR (1H, 19F{1H}, 31P{1H} and 119Sn) spectroscopy. The crystal structure of [SnF3(PMe3)2(OTf)] reveals the three fluorines are in a mer-arrangement with mutually trans PMe3 ligands. The multinuclear NMR spectra confirm this structure is retained in solution, and show that [SnF2(PMe3)2(OTf)2] has trans-phosphines, while [SnF(PMe3)2(OTf)3] has trans PMe3 groups and hence mer-triflate ligands. The [SnF4-n(PMe3)2(OTf)n] are unstable in solution and the decomposition products include [Me3PF]+ and the tin(II) complexes [Sn(PMe3)2(OTf)2] and [Sn3F5(OTf)], both of the latter identified by their crystal structures. The reaction of trans-[SnF4(PiPr3)2] containing the bulkier phosphine, with one and two equivalents of TMSOTf produced unstable mono- and bis-triflates, which the NMR data also suggest contain weakly coordinated triflate, [SnF3(PiPr3)2(OTf)] and [SnF2(PiPr3)2(OTf)2], again with axial phosphines, although some OTf dissociation from the former to give [SnF3(PiPr3)2]+ may occur in solution at room temperature. The new phosphine complexes of SnF4, trans-[SnF4(PiPr3)2] and (cis) [SnF4(κ2-triphos)] (triphos = CH3C(CH2PPh2)3) have also been fully characterised, including the crystal structure of [SnF4(κ2-triphos)]. Attempts to promote P3-coordination by further treatment of this complex with TMSOTf were unsuccessful. The [SnF4(L)2] (L = dmso, py, pyNO, DMF, OPPh3) complexes, which exist as mixtures of cis and trans isomers, react with one equivalent of TMSOTf, followed by addition of one equivalent of L, to form the ionic [SnF3(L)3][OTf] complexes, which were characterised by microanalysis, IR and multinuclear NMR spectroscopy. In nitromethane solution they are a mixture of mer and fac isomers based upon multinuclear NMR data (1H, 19F{1H}, 119Sn). Reaction of [SnF4(OPPh3)2] with two equivalents of TMSOTf and further OPPh3 produced [SnF2(OPPh3)4][OTf]2, which is a mixture of cis and trans isomers in solution. The crystal structure of [SnF2(OPPh3)4][OTf]2 confirms the trans isomer in the solid state, with the triflate ionic. These complexes are rare examples of fluorotin(IV) cations with neutral monodentate ligands.

A pyridyl-triazine complex of Co(II): spectroscopic, structural, and docking studies

A new cobalt(II) complex of 5-phenyl-3-(pyridin-2-yl)-1,2,4-triazine (PPTA), [Co(PPTA)2(NO3)2] (1), is prepared and identified by the elemental analysis, FTIR spectroscopy, and single crystal X-ray diffraction. The single crystal X-ray diffraction analysis of 1 reveals an octahedrally coordinated cobalt(II) complex containing two chelating N2-donor PPTA and two O-donor nitrato ligands in trans-conformation. In addition to hydrogen bonds in the crystal network of 1, there are π—π stacking interactions between aromatic rings of the adjacent complex molecules (pyridine⋯pyridine and pyridine⋯triazine). The ability of complex 1 to interact with nine selected biomacromolecules (BRAF kinase, CatB, DNA gyrase, HDAC7, rHA, RNR, TrxR, TS, Top II) is investigated by docking studies. The results show that in many cases, the studied compound can interact with proteins better than doxorubicin.

Facile synthesis of 2D nanoflakes and 3D nanosponge-like Ni1−xO via direct calcination of Ni (II) coordination compounds of imidazole and 4-nitrobenzoate: Adsorptive separation kinetics and photocatalytic removal of Amaranth dye contaminated wastewater

This study reports a simple method of direct calcination of Ni (II) coordination compounds with N-donor and O-donor ligands such as imidazole and 4-nitrobenzoate to form 2D and 3D Ni1−xO nanostructures. Controlled calcination of imidazole coordinated compound [Ni(Im)6](4-nba)2.2H2O (I) produced 2D nanoflakes in comparison to 4-nitrobenzoate coordinated compound [Ni(H2O)4(4-nba)2].2H2O which formed Ni1−xO nanosponge. Replacement of four coordinated imidazole ligands in compound I with an equivalent number of 4-nitrobenzoate and water molecules as in [Ni(H2O)2(Im)2(4-nba)2] (II) lead to the collapse of flake-like structure upon combustion with the induction of porosity, confirming the dominant effect of 4-nitrobenzoate ligand to form porous structures of Ni1−xO. Material characterization studies revealed that all Ni1−xO nanostructures exhibit cubic phase wherein increase in surface area, pore-volume, and reduction in particle size from 2D nanoflakes to 3D nanosponge is evident. The adsorptive removal of Amaranth dye as a model pollutant using synthesized Ni1−xO nanostructures exhibited high dye removal efficiency of up to 82.81% in the case of 3D nanosponge. The adsorption process is well explained based on the Sips isotherm model and pseudo-first-order reaction kinetics. Photocatalytic Amaranth dye degradation efficiency of 93.80% in 70 min with highest kapp = 4.04×10−2 min−1 is achieved which is attributed to the high surface area and reduction in charge carrier recombination rate as a result of extensive and robust mesoporous structure.

A pillar-layered metal-organic framework based on pinwheel trinuclear zinc-carboxylate clusters; synthesis and characterization

A novel metal-organic frameworks (MOF), namely ({[Zn3(2,6-NDC)3(dabco)]·6DMF·3H2O} (TMU-13) was synthesized by the reaction of 2,6-naphthalenedicarboxylic acid (2,6-NDC) as the O-donor ligand, 1,4-diazabicyclo [2.2.2] octane (dabco) as the N-donor ligand and Zn(II) nitrate hexahydrate. Single crystal X-ray analysis revealed that TMU-13 exhibited a 3D pillar-layered structure based on pinwheel trinuclear zinc-carboxylate clusters as secondary building unit (SBU) with bcu topology and pore window of 12.7 Å × 5.6 Å. Calcination of the compounds TMU-13 at 500 °C under air atmosphere yield ZnO compound.

Crystal Structure and DFT Calculations of Zn(II)-NN’O Schiff Base Complex

The structure of the ZnII complex with NN’O-donor ligand N-(2-pyridyl)methyl-2-hydroxy-3,5-di-tert-butylbenzaldimine (1H) [Zn(C21H27N2O)2]·3CH3OH is described. The Zn (II) metallic centre presents a five-coordinate environment with a square-pyramidal distorted geometry (τ-factor 0.14). One ligand acts as tridentate and another ligand as bidentate [Zn(1-κ3N,N’,O)(1-κ2N,O)]·3CH3OH. The three methanol solvent molecules interact with the zinc complex by hydrogen-bonds (H-bonds). This structure was modelled with Density Functional Theory (DFT) calculations and a good correlation between the experimental parameters and the calculated ones was obtained. The X-ray diffraction single crystal structure of the Zn(II) complex with NN’O-donor pyridino-imino-phenolate ligand (1H) [Zn(1)2]·3CH3OH is described and compared with the modelled by DFT calculations.