HYDROTHERMAL SYNTHESIS, CRYSTAL STRUCTURE, AND LUMINESCENCE OF A NOVEL TETRANUCLEAR ZINC(II) COMPLEX
A new tetranuclear zinc(II) complex [Zn4(tmphen)4(tbip)4(H2O)4] (1, tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline, H2tbip = 5-tert-butyl isophthalic acid) is hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, elemental analysis, and IR spectroscopy. In complex 1, four tbip2– ligands act as bridges between four neighboring Zn atoms to form an unusual tetranuclear zinc cluster. The clusters are further connected by two types of O—H?O and C—H?O hydrogen bonds, generating a three-dimensional supramolecular structure. Meanwhile, p—p stacking interactions and C—H?p interactions further consolidate the three-dimensional supramolecular framework of 1. In addition, the luminescence measurements reveal that complex 1 exhibits strong fluorescent emissions in the solid state at room temperature.
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In complex 1, four tbip2– ligands act as bridges between four neighboring Zn
atoms to form an unusual tetranuclear zinc cluster. <...> The clusters are further connected by two
types of O—HᄷO and C—HᄷO hydrogen bonds, generating a three-dimensional supramolecular
structure. <...> Meanwhile, — stacking interactions and C—Hᄷ interactions further
consolidate the three-dimensional supramolecular framework of 1. <...> In addition, the luminescence
measurements reveal that complex 1 exhibits strong fluorescent emissions in the solid
state at room temperature. <...> The design and synthesis of coordination polymers is an attractive area of research not only due
to their intriguing structures but also their potential applications in optics, magnetism, gas storage, ion
exchange, catalysis, etc. [ 1—3 ]. <...> The most effective and facile approach to coordination polymers is to
utilize multi-pyridine and dicarboxylate ligands to link metal ions, giving innite frameworks [ 4—6 ]. <...> Owing to an excellent coordination ability and a large conjugated system, 1,10-phenanthroline
(phen) has been widely used to build coordination polymers [ 7, 8 ]. <...> Since carboxylate groups have an
excellent coordination ability and flexible coordination patterns, isophthalic acid has also been widely
used in the construction of metal-organic frameworks [ 9, 10 ]. <...> Here, we selected 5-tert-butyl isophthalic acid (H2tbip) as an organic
linker and 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen) as an N-donor chelating ligand, generating
a new Zn(II) coordination complex [Zn4(tmphen)4(tbip)4(H2O)4] 1. <...> An emission spectrum was recorded on a Hitachi F-4500 fluorescence spectrophotometer,
using a slit width of 5 nm excitation at room temperature for the solid samples. <...> All non-hydrogen atoms were located in difference Fourier maps and refined anisotropically. <...> All H atoms were refined isotropically with the isotropic vibration parameters related to the nonH atom to which they are bonded. <...> The structure of complex 1 features a centrosymmetric tetranuclear Zn(II) cluster unit. <...> As shown in Fig. 1, complex 1 crystallizes in the triclinic space group 1P with an asymmetric unit comprising two crystallographically distinct divalent zinc atoms (Zn1, Zn2), two doubly deprotonated bridging tbip dianions (type A, O1 <...>
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