A 3D Hybrid Praseodymium–Antimony–Oxochloride Compound: Single‐Crystal‐to‐Single‐Crystal Transformation and Photocatalytic Properties

Abstract

A 3D organic-inorganic hybrid compound, (2-MepyH)3[{Fe(1,10-phen)3}3][{Pr4Sb12O18(OH)Cl(11.5)}(TDC)(4.5)({Pr4Sb12O18(OH)Cl(9.5)} Cl)]·3(2-Mepy)·28H2O (1; 2-Mepy=2-methylpyridine, 1,10-phen=1,10-phenanthroline, H2TDC=thiophene-2,5-dicarboxylic acid), was hydrothermally synthesized and structurally characterized. Unusually, two kinds of high-nuclearity clusters, namely [(Pr4Sb12O18(OH)Cl11)(COO)5](5-) and [(Pr4Sb12O18(OH)Cl9)Cl(COO)5](4-), coexist in the structure of compound 1; two of the latter clusters are doubly bridged by two μ2-Cl(-) moieties to form a new centrosymmetric dimeric cluster. An unprecedented spontaneous and reversible single-crystal-to-single-crystal transformation was observed, which simultaneously involved a notable organic-ligand movement between the metal ions and an alteration of the bridging ion in the dimeric cluster, induced by guest-release/re-adsorption, thereby giving rise to the interconversion between compound 1 and the compound (2-MepyH)3[{Fe(1,10-phen)3}3][{Pr4Sb12O18(OH)Cl(11.5)}(TDC)4({Pr4Sb12O18Cl(10.5)(TDC)(0.5)(H2O)(1.5)}O(0.5))]·25H2O (1'). The mechanism of this transformation has also been discussed in great detail. Photocatalytic H2-evolution activity was observed for compound 1' under UV light with Pt as a co-catalyst and MeOH as a sacrificial electron donor.

Krebs-Type {M2(WO2)2[B-β-SbW9O33]2}n− (M = SbIII, (WO3)) Tungstoantimonate Possessing Unique Pseudo-Seesaw Sb–O Structure

“…Therefore, the pseudo-seesaw configuration might be a better description for this coordination environment of {Sb(3)­O 4 }. Moreover, we performed statistics on compounds with similar characteristics in the CCDC database, − and the results also met the above speculation (statistical results are shown in Table S4). As a result, the coordination environment of the Sb(3) atom should be between four- and six-coordinated.…”

Structural Evolution and Properties of Praseodymium Antimony Oxochlorides Based on a Chain-like Tertiary Building Unit

“…Without additional linkers, isolated 1-D chain-like anions are evidenced in 1 , while additional Pr-Cl-Pr bridges in 2 and Pr-Cl 2 -Pr, as well as unique Pr-Cl-Sb 3 O 3 bridges in 3 , lead to 2-D and 3-D TBU-based networks, respectively. Unlike the previously reported {Pr 4 Sb 12 } cluster–organic structures [ 24 , 25 , 26 ], in which the linkers are bi/tri functional organic ligands, herein, the title structures are formed through interconnections of TBUs by inorganic linkage units, such as Pr-Cl-Pr and Pr-Cl-Sb 3 O 3 . This is also different from the case in the assembly of single-crystalline superstructures we just reported, in which the (FeCN 6 ) and/or the Ac (acetate group) function as linkers along with Cl − to realize the aggregation of eight {Pr 4 Sb 12 } clusters into supercluster TBUs rather than chain-like TBUs in this work.…”

“…Interchain linking via sharing a Cl bridge (Cl(5)) between a Pr atom of the {Pr 4 Sb 12 } cluster in one layer and a (Sb 3 O 3 ) unit of the {Pr 4 Sb 12 } cluster from another layer finally creates a 3-D porous framework, with a channel of 11.29 × 11.29 Å 2 along the c -axis ( Figure 3 b,c). The connection of Pr-Cl-Sb 3 O 3 is firstly found in the {Pr 4 Sb 12 } cluster-based structures [ 23 , 24 , 25 , 26 ]. Hydrated protons act as cations, and as well as ethanol solvent molecules, are located in the 1-D channels along the c -axis.…”

“…We have reported the first discrete lanthanide antimony nanocluster of [Pr 4 Sb 12 O 18 Cl 17 ] 5− (denoted as {Pr 4 Sb 12 }) with T d symmetry and 12 terminally coordinated Cl − ions as antennas in the cluster [ 23 ]. Subsequently, by changing the reaction conditions and introducing organic carboxylic acid ligands as bridging linkers to replace the terminally coordinated Cl − ions, the {Pr 4 Sb 12 } clusters could act perfectly as SBUs to assemble diversiform compounds with one-dimensional (1-D) helical chain-like, ribbon-like, or tubular structure; two-dimensional (2-D) layered structure; and three-dimensional (3-D) interspersed or porous structure [ 24 , 25 , 26 ]. Very recently, we have isolated two giant superclusters in the form of the Rubik’s cube by eight-aggregation of {Pr 4 Sb 12 } clusters as SBUs, and the superclusters further acted as TBUs to construct a series of superstructures [ 8 ].…”

Detailed Investigation of the Structural, Thermal, and Electronic Properties of Gold Isocyanide Complexes with Mechano‐Triggered Single‐Crystal‐to‐Single‐Crystal Phase Transitions

“…SCSC phase transitions are generally scarce because of the high‐quality ordering of the molecules in the crystal and the macroscopic integrity has to be retained throughout the phase transition. Owing to recent developments in single‐crystal X‐ray diffraction instruments, an increasing number of the SCSC phase transitions have been reported . This special phase transition phenomenon is highly attractive because the detailed molecular arrangements before and after the phase transition can be fully elucidated by single‐crystal X‐ray crystallography.…”