Hydrothermal Approach for Reticular Synthesis of Coordination Assemblies with Dicarboxylatotetramethyldistannoxanes as the Secondary Building Units

Abstract

Hydrothermal reaction of trimethyltin chloride with 1,2,4,5‐benzenetetracarboxylic acid (H4L1), 2,3‐pyridinedicarboxylic acid (H2L2) or 1,4,5,8‐naphthalenetetracarboxylic acid 4,5‐anhydride (H2L3) under optimized pH (5–6) and temperature (130 °C) results in the isolation of new dicarboxylatotetramethyldistannoxane‐based two‐/three‐dimensional coordination assemblies, [{Me2Sn(L1)0.25}2O] (1, 2 as supramolecular isomers), [{Me2Sn(L2)0.5}2O] (3) and [{Me2Sn(L3)0.5}2O] (4). The reaction in each case proceeds with selective cleavage of Sn–C bond. Analogous reaction of trimethyltin chloride with H4L1 at 100 °C affords [Me3Sn(L1)0.25] (5). The supramolecular coordination isomers 1 and 2 with cds and lvt network topologies, respectively are the first representatives among the distannoxane family; the latter confers large solvent accessible voids of 37 % per unit cell. The formation of ladder distannoxane, [{Me2Sn(O2C)}2O]2 as a common structural motif in 1, 3 and 4 is a manifestation of a predefined geometry of the inorganic secondary building unit (SBU) and follows the benchmark of reticular chemistry approach. The coordination assembly, 5 adopts an eight‐connected uninodal net that belongs to bcu topology. These are thermally stable up to 250–400 °C and retain their crystallinity even after exposure to hydrothermal treatment for 24 h.

Naphthalene-1,8-dicarboxylate based zinc coordination polymers: a photophysical study

“…The in situ formation of ntca 2− during the synthesis of coordination polymers has been previously reported showing catalytic and photoluminescence properties. 41–44 Yellow crystals of compound 2 were obtained by slowly decreasing the temperature of a DMF solution after 24 hours at 368 K. Crystal structure of 2 is formed by pairs of tetrahedrally coordinated Zn( ii ) atoms bridged by μ 2 -OH groups (Zn–O distances 1.893(8)–1.931(9) Å) and by L 3− ligand through two monodentate carboxylates (Zn–O distances 1.958(8)–1.99(1)). The pairs of Zn( ii ) atoms are further linked in the (010) direction to other Zn pairs by 5-amino-tetrazolate molecules with Zn–N distances ranging from 1.98(1)–2.02(1) Å. Tetrazolate groups of an adjacent L 3− ligand complete the tetrahedral Zn( ii ) coordination sphere (Zn–N distances 2.02(1)–2.05(1) Å), forming an anionic 2D tape coordination polymer expanded in the (110) plane (Fig.…”

“…The in situ formation of ntca 2− during the synthesis of coordination polymers has been previously reported showing catalytic and photoluminescence properties. [41][42][43][44] Yellow crystals of compound 2 were obtained by slowly decreasing the temperature of a DMF solution after 24 hours at 368 K. Crystal structure of 3 is formed by pairs of tetrahedral Zn(II) metal centres bridged by pairs of monodentate carboxylates from two L 3− ligands (Zn-O distances range from 1.89(1)-2.036(3) Å) (Fig. 3).…”

Supramolecular Assemblies and Reversible De‐/ Rehydration in One‐Dimensional Dimethyltin Carboxylates

“…[8][9][10] Recent studies from our group have been directed to explore hydrothermal approach for the synthesis of two-/threedimensional dimethyltin carboxylates derived from polytopic carboxylic acids. [11] The formation of these assemblies requires careful screening of the pH (2-8) and temperature (100-130 °C) of the reaction medium. An interesting outcome emanating from these studies is the realization of reticular synthesis based on dimeric dicarboxylatotetramethyldistannoxane, [{Me 2 Sn-(O 2 CÀ )} 2 O] 2 as the secondary building unit (SBU).…”

Synthesis and Structural Characterization of New Ladder Organostannoxanes Derived from Sulfonic Acid Derivatives

“…Ladder-shaped tetranuclear organotin compounds [11,6,12], have been isolated. Many butylstannoxanes were prepared using carboxylates ligands [9,11,13,14] [6] and [(n-C 4 H 9 ) 2 Sn{OSO 2 C 6 H 3 (CH 3 ) 2 -2,5} 2 ] (centrosymmetric dimer) [15]. The aim of the present contribution was to prepare and characterize organostannoxane-type structures from sulfonates, [n-Bu 2 Sn] 4 (µ 3 -O) 2 (µ 2 -OH) 2 (OSO 2 R) 2 (R=4-HO-C 6 H 4 -and CH 3 -).…”