Amide-Driven Secondary Building Unit Structural Transformations between Zn(II) Coordination Polymers

Ejarque, Daniel; Calvet, Teresa; Font-Bardı́a, Mercè; Pons, Josefina

doi:10.1021/acs.cgd.2c00520

Cited by 20 publications

(10 citation statements)

References 104 publications

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“…Although this event is rather rare, there are some reports about it. In a few interesting cases, supramolecular isomers were formed in the reaction vessel concomitantly. − Although structural transformation of CPs in the solid phase is highly regarded, − there are few studies on the structural transformation in the liquid phase in CPs, especially through dissolution–recrystallization structural transformation (DRST). ,,,− …”

Section: Introductionmentioning

confidence: 99%

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Water Content-Controlled Formation and Transformation of Concomitant Pseudopolymorph Coordination Polymers

2023

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Two concomitant pseudopolymorph coordination polymers {[Cd2L2(OAc)4]·2DMSO} n (1) and {[CdL(OAc)2]·2.75H2O} n (2) were synthesized by self-assembly of 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene (L) and cadmium acetate in DMSO. Single-crystal X-ray diffraction confirmed that 1D ladder structural motifs exist for pseudopolymorphs 1 and 2 which contain DMSO and water guest molecules, respectively. Our study illustrated the active role of solvent water content in obtaining compound 2. We find that the presence of water as an impurity in the DMSO solvent creates the possibility of formation of concomitant pseudopolymorph coordination polymers which is a unique event. Furthermore, our analyses showed the effect of environmental humidity on the transformation of unstable compound 1. 1D ladder pseudopolymorphic compound 1 could be transformed to guest-free 1D linear compound [CdL(OAc)2(H2O)] n (3′) (the powder form of single crystals of 3) through a scarce case of water absorption from air. Also, the crystalline material of coordination polymer 3 was transformed to coordination polymer 2 through the dissolution–recrystallization structural transformation process in DMF or DMSO. Our study clarified that the amount of water in the reaction container can control the formation of one of the compounds 2 or 3. In the presence of a significant amount of water, compound 3 (coordinated water) will be produced, whereas if a small amount of water is present, compound 2 (uncoordinated water) is prepared as an exclusive product.

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Section: Introductionmentioning

confidence: 99%

“… 44 − 47 Although structural transformation of CPs in the solid phase is highly regarded, 48 − 56 there are few studies on the structural transformation in the liquid phase in CPs, especially through dissolution–recrystallization structural transformation (DRST). 23 , 28 , 36 , 57 − 60 …”

Section: Introductionmentioning

confidence: 99%

Water Content-Controlled Formation and Transformation of Concomitant Pseudopolymorph Coordination Polymers

2023

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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%

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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“…To date, only one dihydrate and one cocrystal have been reported. − The dihydrate structure connected the HACA molecules through masked synthons of water clusters supported by acid···amide interactions, , whereas the cocrystal contained 2-pyridone (Pdon), presenting Pdon···acid and amide···amide synthons . However, previous studies performed in the group with coordination compounds suggested a tendency of the HACA molecules toward being ordered by amide···amide patterns, leading to supramolecular chains or cycles depending on the synthetic conditions. − …”

Section: Introductionmentioning

confidence: 99%

Structural Landscape of α-Acetamidocinnamic Acid Cocrystals with Bipyridine-Based Coformers: Influence of Crystal Packing on Their Thermal and Photophysical Properties

Ejarque,

Calvet,

Font-Bardia

et al. 2024

Crystal Growth & Design

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Controlling the supramolecular synthon outcome in systems with different functionalities has been a key factor for the design of supramolecular materials, which also affected their physicochemical properties. In this contribution, we have analyzed the structural landscape of α-acetamidocinnamic acid (HACA) aiming to find its synthon outcome from the competitivity between its acidic and amidic groups. We prepared four multicomponent forms including one dihydrate (HACA•2H 2 O) and three cocrystals bearing different bipyridine coformers with formulas (HACA) 2 (1,2-bpe) (1), (HACA) 2 (4,4′-azpy) (2), and (HACA) 2 (4,4′-bipy) 3 (3) (1,2-bpe = 1,2-bis(4-pyridyl)ethylene; 4,4′-azpy = 4,4′-azopyridine; 4,4′-bipy = 4,4′-bipyridine). First, we applied a virtual screening approach to assess the feasibility of cocrystal formation. Then, we synthesized the cocrystals, via liquid-assisted grinding (LAG) (1 and 2) or solvothermal (3) techniques, and single crystals of HACA, and their four multicomponent forms were obtained showing different synthons and crystal packings. Besides, a Cambridge Structural Database (CSD) search of the cocrystals presenting bipyridine-type coformers and molecules with acid and amide functionalities was performed, and the observed synthon occurrences as well as the possibility of synthon modification by tuning the H-donor/H-acceptor propensity of the acidic and amidic groups were shown. Finally, we measured their thermal and photophysical properties, which were correlated with their structural features.

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Amide-Driven Secondary Building Unit Structural Transformations between Zn(II) Coordination Polymers

Cited by 20 publications

References 104 publications

Water Content-Controlled Formation and Transformation of Concomitant Pseudopolymorph Coordination Polymers

Water Content-Controlled Formation and Transformation of Concomitant Pseudopolymorph Coordination Polymers

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

Structural Landscape of α-Acetamidocinnamic Acid Cocrystals with Bipyridine-Based Coformers: Influence of Crystal Packing on Their Thermal and Photophysical Properties

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