Incorporating the Thiazolo[5,4-d]thiazole Unit into a Coordination Polymer with Interdigitated Structure

Abstract

Abstract:The linker 2,5-di(4-pyridyl)thiazolo [5,4-d]thiazole (Dptztz), whose synthesis and structure is described here, was utilized together with benzene-1,3-dicarboxylate (isophthalate, 1,3-BDC 2− ) for the preparation of the two-dimensional coordination network [Zn(1,3-BDC)Dptztz]·DMF (DMF = dimethylformamide) via a solvothermal reaction. Compound [Zn(1,3-BDC)Dptztz]·DMF belongs to the class of coordination polymers with interdigitated structure (CIDs). The incorporated DMF solvent molecules can be removed through solvent exchange and evacuation such that the supramolecular 3D packing of the 2D networks retains porosity for CO 2 adsorption in activated [Zn(1,3-BDC)Dptztz]. The first sorption study of a tztz-functionalized porous metal-organic framework material yields a BET surface of 417 m 2 /g calculated from the CO 2 adsorption data. The heat of adsorption for CO 2 exhibits a relative maximum with 27.7 kJ/mol at an adsorbed CO 2 amount of about 4 cm 3 /g STP, which is interpreted as a gate-opening effect.

Thiazolothiazole-Based Luminescent Metal–Organic Frameworks with Ligand-to-Ligand Energy Transfer and Hg2+-Sensing Capabilities

“…The calculated minimum and maximum transmission coefficients were 0.8214 and 1.0000. The structure was solved and refined using space group Iba 2, with Z = 8 for the formula unit C 47 H 31 N 9 O 9 S 4 Zn 2 . , The final anisotropic full-matrix least-squares refinement on F 2 with 641 variables converged at R1 = 4.40% for the observed data and wR2 = 8.87% for all data. The goodness-of-fit was 1.017.…”

“…Briefly, a solution mixture of dithiooxamide (200 mg, 1.66 mmol) and 4-pyridinecarboxaldehyde (0.4 mL, 4.4 mmol) in anhydrous DMF (10 mL) was heated under reflux for 2.5 h. Upon cooling of the reaction mixture to room temperature, a yellow crystalline product precipitated out, which was collected by filtration, washed with H 2 O and MeOH, and dried under air (311 mg, 63% yield). The 1 H NMR spectrum of the product was in good agreement with that of DPTTZ reported in literature …”

“…Therefore, there remains a need for porphyrin-free luminescent MOFs that can support energy transfer and display stimuli-responsive emission changes. Diversifying the composition, properties, and functions of light-harvesting MOFs, herein, we report synthesis, PL behavior, and energy transfer and Hg 2+ sensing capabilities of a new pillared-paddle wheel framework Zn 2 (NDC) 2 (DPTTZ) featuring 2,6-naphthalele dicarboxylate (NDC) struts and N , N′ -di­(4-pyridyl)­thiazolo-[5,4- d ]­thiazole (DPTTZ) pillars (Figure ), which are excellent chromophores and fluorophores with complementary absorption and emission characteristics suitable for Förster resonance energy transfer (FRET). , Although the redox and light-harvesting properties of electron deficient and luminescent TTZ compounds are well documented in molecular environments, , they have been rarely incorporated in MOFs − and their PL and redox properties have yet to be explored inside crystalline frameworks. The lowest-energy absorption peak of DPTTZ overlaps quite well with the emission peak of NDC, which enables ligand-to-ligand FRET and allows the MOF to display exclusively DPTTZ-centric blue emission (∼410 nm) irrespective of the excitation wavelength.…”

Enabling Control over Mechanical Conformity and Luminescence in Molecular Crystals: Interaction Engineering in Action

“…Pyridine‐appended thiazolothiazole derivative 2,5‐di(pyridin‐4‐yl)thiazolo[5,4‐ d ]thiazole (PyTTZ) was synthesized by a condensation reaction between dithiooxamide and 4‐pyridinecarboxaldehyde in DMF (Scheme S1, in the Supporting Information) [11c, 13] . Two polymorphic forms were prepared from DMSO solution by the interplay between thermodynamic and kinetic factors of crystallization.…”

A series of 1-D zinc(II) coordination polymers with 3-D supramolecular networks: synthesis, structural investigation, and NBO analysis

“…In this context, 4,4 0 -bipyridine analogue ligands are important multidentate N,N 0 -donor ligands because of their excellent coordination ability and distinctive structural properties. In combination with metal cations, the variable intraligand geometry, the versatility in the spacer part and the influence on the packing process through intermolecular p-p interactions have led to networks with unusual structures and prominent architectures [7][8][9]. N,N 0 -Bis(pyridin-4-ylmethylene)naphthalene-1,5-diamine represents an attractive spacer for the synthesis of coordination polymers.…”