A rod-like hexanuclear nickel cluster based on a bi(pyrazole-alcohol) ligand: structure, electrospray ionization mass spectrometry, magnetism and photocurrent response

Sheng, Kai; Ji, Bao-Qian; Feng, Lei; Su, Yan-Min; Jagodič, Marko; Jagličić, Zvonko; Sun, Di

doi:10.1039/d0nj00959h

Cited by 9 publications

(5 citation statements)

References 36 publications

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“…4 has a peak photocurrent at a voltage of 0.32 V, I no filter = 7.41 × 10 –5 mA cm –2 , I 400–760 nm = 6.17 × 10 –5 mA cm –2 , I 313 nm = 4.21 × 10 –5 mA cm –2 , I 350 nm = 3.56 × 10 –5 mA cm –2 , and I 400 nm = 3.21 × 10 –5 mA cm –2 . The diverse structural compositions and molecular packings of 3 and 4 may be the causes of the alteration in the photocurrent densities. − …”

Section: Resultsmentioning

confidence: 99%

Copper(I) Alkynyl Clusters with Crystallization-Induced Emission Enhancement

et al. 2021

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Four copper(I) alkynyl complexes incorporating phosphate ligands, namely, [Cu16( t BuCC)12(PhOPO3)2] n (1; PhOPO3 = phenyl phosphate), [Cu16( t BuCC)12(1-NaphOPO3)2] n (2; 1-NaphOPO3 = 1-naphthyl phosphate), [VO4@Cu25( t BuCC)19(1-NaphOPO3)](PF6)0.5(F)0.5 (3), and [PO4@Cu25( t BuCC)19(1-NaphOPO3)](PF6)0.5(F)0.5 (4), were solvothermally synthesized and well-characterized by IR spectroscopy, powder X-ray diffraction, and single-crystal X-ray diffraction. Single-crystal X-ray analysis revealed that the Cu16 cluster-based coordination chain polymers 1 and 2 are formed by assembly during crystallization, while 3 and 4 contain high-nuclearity copper(I) composite clusters enclosing orthovanadate and phosphate template ions, respectively, that are supported by ROPO3 2– ligands. Complexes 1–4 exhibit crystallization-induced emission enhancement. Their crystalline state shows strong luminescence, in striking contrast to the weak emission of the amorphous state and solution phase. A detailed investigation of the crystal structure suggests that well-arranged C–H···π and π···π interactions between the ligands are the major factors for this enhanced emission. Clusters 3 and 4 also exhibit photocurrent responses upon visible-light illumination.

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Section: Resultsmentioning

confidence: 99%

Copper(I) Alkynyl Clusters with Crystallization-Induced Emission Enhancement

et al. 2021

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“…12−20 In view of the divergence of the chelating ends, we have recently been exploring the coordination chemistry of bdped ligand to generate polymeric structures. 21,22 These works followed the initial coordination chemistry of dipyridyl-ketone and its derivatives. Given the importance of copper in the glyoxylate metabolism, it is beneficial to explore its coordination chemistry with glyoxal containing ligands.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The structure of H 2 bdped has been deposited at CCDC in a previous work but not discussed. 21,22 Here, we briefly describe the structure in relation to those of the clusters. It appears that due to the large 3,5-dimethyl-pyrazole groups it adopts a staggered conformation about the ethane C−C bond looking like a 90°Z.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Its reaction with CuCl 2 ·2H 2 O in ethanol resulted in two different complexes, [Cu(H 2 bdped)Cl 2 ] and [Cu 2 (H 2 bdped)Cl 4 ] . Other derivatives where the 3,5-dimethyl-pyrazole has been replaced by pyrazole, benzotriazole, and imidazole were reported using the coupling reaction with glyoxal. , However, only minor details of their complexations with transition metals are known, and no structural details are available. − In view of the divergence of the chelating ends, we have recently been exploring the coordination chemistry of bdped ligand to generate polymeric structures. , These works followed the initial coordination chemistry of dipyridyl-ketone and its derivatives. Given the importance of copper in the glyoxylate metabolism, it is beneficial to explore its coordination chemistry with glyoxal containing ligands.…”

Section: Resultsmentioning

confidence: 99%

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Copper(II)-Assisted Ligand Fragmentation Leading to Three Families of Metallamacrocycle

Jagodič

et al. 2020

Inorg. Chem.

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We present an unprecedented copper(II)-assisted organic ligand fragmentation process under basic conditions leading to several ligands within three families of metallamacrocycle, Cu 6 , Cu 8 , and Cu 16 . The sequential multistep reaction include (i) the deprotonation of the starting alcohol, 1,2-bis(3,5-dimethyl-pyrazol-1-yl)ethane-1,2-diol (H 2 bdped) to its diolate bdped followed by complexation through six bonds (μ 6 ) to three copper atoms in a ring, (ii) the breaking of the ethane-pyrazole C−N bonds by the different solvent alcohols to form 1-(3,5-dimethyl-pyrazol-1-yl)-2-methoxyethane-1,2-diolate (dpmed) or 2-(3,5-dimethyl-pyrazol-1-yl)-2-hydroxyacetate (dpet), while retaining coordination to the copper centers and (iii) the final step to ethane-1,1,2,2-tetraolate, C 2 H 2 O 4 4− (et). Importantly, the latter product, only observed on two previous occasions, occupies the core of Cu 6 and Cu 16 through exceptionally eight coordination bonds (μ 8 ). Its alkyl esters, 2-alkoxyethane-1,1,2triolate (met, eet, and pet), also occupy the central parts of Cu 8 but forming six bonds (μ 6 ) instead. The other product, 3,5-dimethylpyrazolate (dp), acts as peripheral bridges (μ 2 ) but it is not involved in coordination if the starting salt is copper acetate, this may be a consequence of acetate being a better μ 2 -chelating ligand. In the presence of an oxidizing agent, K 2 Cr 2 O 7 , C 2 H 2 O 4 4− (et) is oxidized to oxalate, C 2 O 4 2− (ox). Thus, an additional μ 3hydroxide and μ 4 -oxalate in Cu 16 widen the complexity of the structures, not to mention the range of coordination geometries of the copper centers, though in the present cases they can be classed in only two types: distorted square-planar and square-pyramid. In addition to single-crystal crystallography, the results from different techniques such as IR, ESI-MS, optical UV−vis, and SQUID magnetometry help in the characterization of these rare metallamacrocycles made from unexpected and in situ generated ligands. We believe the results of the organic transformations are highly relevant to von Liebig's benzil−benzilic acid rearrangement.

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“…Various types of materials with interesting structures and good performance have been produced by employing ligands containing multidentate coordination sites such as carboxylate, pyridyl, Schiff base and other donors, to assembly transition metal cations including Zn(II), Cd(II), Co(III), Ni(II), Cu(I)/Cu(II) and Mn(II). [5][6][7][8][9][10][11] Coating semiconductive substrates with organic dyes can be an effective method to improve the photoelectric performances of these materials for applications including dye-sensitized solar cells [12][13][14] and chemolumines-cence sensors. [15,16] Many CPs absorb organic dyes and the resulting composites exhibit improved photoelectric responses.…”

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confidence: 99%

New Silver(I)‐P4 Coordination Polymers Strongly Adsorb Congo Red to Yield Composites with Enhanced Photocurrent Responses

et al. 2021

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Reaction of tetraphosphine (P4) ligand dppbpda with Ag(I) oxylates yielded new coordination polymers (CPs) of formula [(dppbpda)Ag4(Ox)4]n (Ox=Bz (1), Sal (2), LA (3), Bz=benzoate, Sal=salicylate, LA=lactate). The solid‐state structures of 1–3 consist of one dimensional (1D) chains constructed from tetranuclear μ‐η2,η2‐ connected Ag4(Ox)4 cluster cores and dppbpda bridging ligands. Compounds 1–3 absorbed Congo Red in two distinct steps, with maximum uptake quantities of 1438 (1), 1417 (2) and 1656 (3) mg/g, inversely correlating with the size of the anions in the CPs. These CPs had band gaps in the semiconducting region (Eg) 3.05–3.15 eV and all three showed enhanced two‐peak photocurrent responses during the stepwise adsorption of CR, with maximum photocurrent densities of 227 (1), 163 (2) and 386 (3) μA cm−2 for composites with optimized dye coverage.

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A rod-like hexanuclear nickel cluster based on a bi(pyrazole-alcohol) ligand: structure, electrospray ionization mass spectrometry, magnetism and photocurrent response

Abstract: An unusual one-dimensional zig-zag hexanuclear Ni(ii) cluster has been easily and successfully constructed using a designed multidentate pyrazole-alcohol ligand.

Cited by 9 publications

References 36 publications

Copper(I) Alkynyl Clusters with Crystallization-Induced Emission Enhancement

Copper(I) Alkynyl Clusters with Crystallization-Induced Emission Enhancement

Copper(II)-Assisted Ligand Fragmentation Leading to Three Families of Metallamacrocycle

New Silver(I)‐P4 Coordination Polymers Strongly Adsorb Congo Red to Yield Composites with Enhanced Photocurrent Responses

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