Ligand-driven self-assembly of iodine-based Cd(<scp>ii</scp>) complexes <i>via</i> dissolution–recrystallization structural transformation

Tunsrichon, Sujitra; Youngme, Sujittra; Boonmak, Jaursup

doi:10.1039/d2ce00395c

Cited by 3 publications

(4 citation statements)

References 41 publications

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“…Herein, the spectra are broad without vibronic progressions. According to previous reports about polynuclear Cu(I) clusters, ,,,− the observed emission can be assigned to the metal-to-ligand (d 10 Cu → π* dppy) charge-transfer (MLCT) state.…”

Section: Resultsmentioning

confidence: 65%

“…To date, it is still difficult to accurately predict the target structure of mixed-ligand-based multicore coordination complexes under the current crystallization techniques, mainly owing to the lack of a deeper understanding of the crystal growth process and various experimental parameters that influence their structures. Therefore, identifying the crystal structures of thermodynamic and dynamic products as well as the structural transformation process could provide important hints for the controllable synthesis of functional multicore coordination compounds. − …”

Section: Introductionmentioning

confidence: 99%

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Controllable Preparation and Direct Observation of an Interconversion between Kinetically and Thermodynamically Stable Luminescent Multicuprous Coordination Complexes

Cao,

Li,

Tan

et al. 2024

Crystal Growth & Design

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We report the controlled preparation of kinetically and thermodynamically luminescent multinuclear cuprous coordination complexes. On reaction of the bidentate P/N-ligand (2-(diphenylphosphino)pyridine, abbreviated as dppy) and copper(I) with a similar stoichiometry but in different concentration conditions at ambient temperature, hexagonal crystals of [Cu 2 (μ-dppy) 3 Cl]PF 6 •CH 2 Cl 2 (1) or polyhedron crystals of [Cu 4 (μ-dppy) 6 Cl](PF 6 ) 3 (2) were formed as kinetic or thermodynamic products, respectively. Investigation of the structures, morphologies, theoretical calculation, and photophysical properties of the multinuclear cuprous coordination complexes demonstrates the formation of and differences between kinetically and thermodynamically stable conformations. Single-crystal X-ray structural analyses indicated that 1 features the head-to-head orientation dppy bridged dinuclear trefoil-like Cu 2 -core with one terminal Cl − , and tetranuclear 2 can be regarded as a Cl − bridged dimer of 1 with two-third flipping head-to-tail dppy ligands. The density functional theory (DFT) calculations demonstrated that 2 had a lower frontier molecular orbital energy than 1, with an energy difference of 320.76 kJ/mol. Intriguingly, the controllable reversible transformation between 1 and 2 can be achieved under suitable conditions. By soaking the crystal in the mother liquor or alcohol, the kinetically stable 1 can slowly transform to the thermodynamically stable 2, or conversely, 2 can also quickly reconstruct to 1 when it is soaked in a chloride solution. Steadily changing morphologies, photoluminescence, as well as powder X-ray diffraction patterns were observed during the gradual transformation process. Based on structural analyses, a feasible transforming mechanism was proposed. The energetic and structural analyses of and the interconversion process between kinetically and thermodynamically stable multicuprous complexes here provide insights into the relations among the structures, morphologies, and properties of the metal−organic coordination materials at the molecular level.

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Section: Resultsmentioning

confidence: 65%

Section: Introductionmentioning

confidence: 99%

Controllable Preparation and Direct Observation of an Interconversion between Kinetically and Thermodynamically Stable Luminescent Multicuprous Coordination Complexes

Cao,

Li,

Tan

et al. 2024

Crystal Growth & Design

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“…We successfully synthesized Cu(II) coordination polymer macromolecules and coordination dimers. Due to the various coordination modes of Cu(II) atoms, the DRST of Cu(II) coordination polymers with unsaturated coordination modes is more easily achieved. − Few studies have directly compared the impact of secondary bonds formed by halogen substituents on the disassembly and reassembly process of supramolecular structures and their influence on electronic properties during the macromolecule-to-oligomer conversion of polymers. This work provides insights into developing convertible dielectric and semiconductor soft materials by leveraging the selective differences of secondary bonds formed by halogen substituents in the disassembly and reassembly process of SAFs, dynamic bond exchange during secondary bond self-repair, and stable primary building units. − …”

Section: Introductionmentioning

confidence: 99%

Utilizing Secondary Bonds Formed by Halogen Substituents: Achieving the Dynamic Transition of Low-Bandgap Semiconductor Polymers from Macromolecules to Small Molecules

Li,

Tuo,

Zhang

et al. 2024

Macromolecules

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Utilizing supramolecular assembly frameworks as soft materials to investigate the dissolution-recrystallization dynamics presents a viable approach for converting Cu(II) coordination polymer macromolecules into dimeric small molecules. We have designed and synthesized four Cu(II) coordination polymers and four coordination dimers, representing macromolecular polymers and oligomeric small molecules, respectively. Interestingly, the introduction of nitrate anions into the macromolecular polymer system can facilitate the conversion to oligomeric small molecules. This process involves dissolutionrecrystallization structural transformation, altering the coordination mode of Cu(II) in the primary building units during the transformation. Moreover, this process entails the disassembly and reformation of the soft supramolecular framework, driven by the dynamic bond exchange of secondary bonds formed by halogen substituents X (F, Cl, Br, and I). These secondary bonds undergo dynamic exchange during the reformation of the supramolecular framework after disassembly. Based on the semiconductor properties of Cu(II) coordination polymers, we compared the electronic properties to evaluate the impact of halogen-substituted secondary bonds on the low-bandgap polymeric semiconductor macromolecules and small molecules of Cu(II).

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“…Under the impact of external stimuli (light, heat, PH, solvents, etc. ), DRST in crystals can be generated. − This mechanism has been more thoroughly studied in porous coordination polymers (PCPs), which have developed into a crystal synthesis method . However, based on many reports about Sn (II)-based or Sn(IV)-based materials separately, they have not been thoroughly studied in OTHHs.…”

Section: Introductionmentioning

confidence: 99%

Oxidation-Induced Dissolution Recrystallization Structural Transformation Strategy Enhanced Nonlinear Optical Effect of Hybrid Chiral Tin Bromide Single Crystals

Yu,

Han,

Liu

et al. 2023

Inorg. Chem.

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Ligand-driven self-assembly of iodine-based Cd(ii) complexes via dissolution–recrystallization structural transformation

Abstract: The iodo-cadmium(II) complexes with a diversity of crystalline architectures have been prepared via a combination of a Cd(II) precursor and varied iodine solutions. The iodo-Cd(II) complexes with 1,10-phenantroline were assembled...

Cited by 3 publications

References 41 publications

Controllable Preparation and Direct Observation of an Interconversion between Kinetically and Thermodynamically Stable Luminescent Multicuprous Coordination Complexes

Controllable Preparation and Direct Observation of an Interconversion between Kinetically and Thermodynamically Stable Luminescent Multicuprous Coordination Complexes

Utilizing Secondary Bonds Formed by Halogen Substituents: Achieving the Dynamic Transition of Low-Bandgap Semiconductor Polymers from Macromolecules to Small Molecules

Oxidation-Induced Dissolution Recrystallization Structural Transformation Strategy Enhanced Nonlinear Optical Effect of Hybrid Chiral Tin Bromide Single Crystals

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