Thiacalixarene-Supported MoNa Clusters: Crystal Transition and Mo-S Coordination on Visible-Light Absorption

Abstract

Here, we report four molybdenum-sodium-based molecular architectures featuring the dinuclear molybdenum units built from p-tertbutylthiacalix[4]arene through solvent-induced assembly. The Mo 8 Na 6 cluster crystallized from a methanol and N,N-dimethylformamide mixed solution, whereas not only an infinite coordination polymer Mo 4 Na 4 but also a cluster Mo 8 Na 8 α were formed simultaneously in sole methanol solvent. Digestion of Mo 8 Na 8 α in dichloromethane, followed by addition of methanol, recrystallized into the Mo 8 Na 8 β cluster, exhibiting conformation transformation of the thiacalix[4]arene. Two unprecedented Mo-S coordination modes displayed in a Mo 2 unit for the four complexes. The clusters

Solvent‐Controlled Condensation of [Mo2O5(PTC4A)2]6− Metalloligand in Stepwise Assembly of Hexagonal and Rectangular Ag18 Nanoclusters

“…The geometry of [(Mo 2 O 5 PTC4A) 6 ] 12− is an annulus and it provides 12 sulfur and 36 oxygen atoms to confine silver atoms in the inner space, resulting in a hexagonal core. The Mo VI metallization of thiacalix[4]arene has been observed, [13] but its further cyclization to form a metallamacrocycle is quite uncommon.…”

“…Notably, this [(Mo 2 O 5 PTC4A) 6 ] 12À metallamacrocycle is formed by condensation of the [Mo 2 O 5 (PTC4A) 2 ] 6À metalloligand and this condensation procedure was also investigated with the aid of ESI-MS. As illustrated in Figure S4a, a series of isotope peaks (3 a-3 r) were observed when we added silver species ([EtSAg] 12À is an annulus and it provides 12 sulfur and 36 oxygen atoms to confine silver atoms in the inner space, resulting in a hexagonal core. The Mo VI metallization of thiacalix [4]arene has been observed, [13] but its further cyclization to form a metallamacrocycle is quite uncommon.…”

Bioorthogonal chemistry of polyoxometalates – challenges and prospects

“…142 In addition, related thiocalixarenes, in the presence of transition metal cations, are able to induce the reassembly of archetypal POM structure into new topologies. [143][144][145][146] Even less information is available about other macrocycles widely used in medicine, cucurbiturils. 147 The Mn-substituted Anderson-Evans-type POMs covalently functionalized with bcucurbituril (b-CB) moieties 148 [MnMo 6 O 18 ((OCH 2 ) 3 -CNH(CO)(CH 2 ) 3 (CO)NH-(b-CB)) 2 ] 3− can interact with surfactant agents of different nature, forming multi-stimuli responsive structured emulsions in two-phase media.…”

A calixarene-based coordination cage as an efficient luminescent sensor for Fe3+, MnO4−, NB and 2,4-DNP in aqueous medium

“…p-tert -Butylthiacalix[4]arene (H 4 TC4A), a macrocyclic compound formed by phenol units and sulfur atoms, can react with metal ions (M = Fe 2+ , Co 2+ , Ni 2+ ) to form shuttlecock-like M 4 -TC4A secondary building units (SBUs). 40–42 M 4 -TC4A SBUs coordinate with auxiliary organic ligands to form larger entities or extended structures. Herein, we report a {Mg 24 } octahedral nanocage ( SWU- 2 ) assembled from Mg 4 -TC4A SBUs and BTC ligands (H 3 BTC = 1,3,5-benzenetricarboxylic acid).…”

“…p-tert-Butylthiacalix [4]arene (H 4 TC4A), a macrocyclic compound formed by phenol units and sulfur atoms, can react with metal ions (M = Fe 2+ , Co 2+ , Ni 2+ ) to form shuttlecock-like M 4 -TC4A secondary building units (SBUs). [40][41][42]…”