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Concomitant Formation of Compositionally Distinct Coordination Polymers Based on a Triacid Linker: Solvent‐Mediated Metamorphosis
Author(s) -
Chandrasekhar Pujari,
Bajpai Alankriti,
Savitha Govardhan,
Moorthy Jarugu Narasimha
Publication year - 2017
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201601100
Subject(s) - chemistry , sbus , linker , solvent , crystallography , metal , polymer , coordination polymer , crystal engineering , stereochemistry , crystal structure , metal organic framework , supramolecular chemistry , organic chemistry , computer science , operating system , adsorption
The solvothermal reaction of the semirigid tritopic ligand 1,3,5‐tris[2,6‐dimethyl‐4‐(α‐carboxy)methoxyphenyl]benzene (H 3 BTA) with Zn(NO 3 ) 2 in a DEF/EtOH/H 2 O (4:2:1 v/v/v, DEF = N , N ‐diethylformamide) mixture leads to the formation of three compositionally distinct coordination polymers (CPs) with different morphologies, that is, rods (Zn‐R), needles (Zn‐N), and blocks (Zn‐B), in the same pot at different concentrations and temperatures. Two sets of compositionally distinct CPs are formed concomitantly at two different reactant concentrations, and one of them is common to the two sets. Attempts to interconvert the three CPs at different temperatures in the same solvent system revealed that the acentric crystals of Zn‐N and Zn‐R convert to the chiral crystals of Zn‐B irreversibly, and the latter remain intact. The crystal‐packing analysis reveals that the three CPs have different Zn 2+ coordination geometries, secondary building units (SBUs), framework structures, and solvent‐accessible volumes; therefore, an interplay of kinetic and thermodynamic factors determines the energetics of the metal‐mediated self‐assembly. The formation of two sets of concomitant compositionally distinct CPs from different concentrations of reactants and the conversion of the achiral crystals to the chiral ones are in agreement with the coordination preferences of the metal ions and the structural flexibility of the semirigid linker, and the solvent system plays a pivotal role.