Synthetic Route to a Triphenylenehexaselenol-Based Metal Organic Framework with Semi-conductive and Glassy Magnetic Properties

Abstract

In the latest decade, two-dimensional (2D) p-d conjugated metal organic frameworks (MOFs) constructed from metal ions with square-planar coordination geometry and benzene-or triphenylenederived ligands with ortho-disubstituted N, O, or S donor atoms have received great research interests because of their exceptional physical properties and promising applications. New MOFs of this class are constantly being reported, but 2D metal bis(diselenolene) MOFs based on organic ligands with ortho-disubstituted Se donor atoms have not been synthesized. Herein, a Lewis-acid-induced dealkylation protocol is introduced to the synthesis of arenepolyselenols and related coordination polymers. A triphenylene-derived diselenaborole compound is synthesized and employed as precursor reagent for the synthesis of 2,3,6,7,10,11-triphenylenehexaselenol (H 6 TPHS) and the first conductive metal organic framework namely Co-TPHS based on triphenylenehexaselenolate (TPHS 6À). Co-TPHS exhibits porous honeycomb 2D structure and electrically conductive and glassy magnetic properties.

Two-dimensional conjugated metal–organic frameworks (2D c-MOFs): chemistry and function for MOFtronics

“…After the first 2D c-MOF reported by Yaghi group in 2012, 19 various ortho-substituted benzene-and triphenylene (TP)-based building blocks have been developed/employed for the formation of 2D c-MOFs, such as 1,2,3,4,5,6-hexahydroxybenzene (HHB), 39 1,2,3,4,5,6-hexaaminobenzene (HAB), 40 1,2,3,4,5,6benzenehexathiol (BHT, also denoted asHTB), 41 1,2,3,4,5,6benzenehexaselenol (HSeB), 42 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP), 19 2,3,6,7,10,11-hexaaminotriphenylene (HATP), 43,44 2,3,6,7,10,11-triphenylenehexathiol (THT, also denoted as HTTP), 45 2,3,6,7,10,11-triphenylenehexaselenol (HSeTP). 46 Larger conjugated monomers have been developed and explored for the synthesis of 2D c-MOFs as well (Fig. 2), e.g.…”

“…28,58 Meanwhile, HTTP-based MS 4 -linked (M = Ni, Co, Fe, Pt) 2D c-MOFs were also developed (mainly as films, see Section 4.2), 45,64,118 and subsequently great efforts have been devoted to the TP-based 2D c-MOF family with the aim of exploring their multifunctional properties. 28,46,59,90,100,106,109,146,147 Towards frameworks with denser distributed ligands and metals, benzene-based ligands were developed. 31,39,40,42,74,135 Typically, in 2017, Dou et al synthesized MN 4 -linked M 3 (HIB) 2 (M = Cu, Ni) 2D c-MOFs by mixing HAB, M 2+ , and NH 3 ÁH 2 O in DMSO, followed by heating at 60 1C for 2 hours.…”

“…linkage were also investigated in few reports. 42,46,[61][62][63] Among these various linkages, Cu and Ni represented the majority of metal nodes, while Fe and Co were widely utilized for the construction of MS 4 . By contrast, the utilization of Zn, Pd, and Pt remains very limited.…”

“…Cu 3 (H-SeB): 110 S cm À1 , Co 3 (HSeTP) 2 : 10 À6 S cm À1 ) than those of MS 4linked bulk 2D c-MOFs (Table 1). 42,46 Varying the functional groups will also vary the coordination bond length between metal nodes and linkers in the MX 4linkages due to the difference of the atom radius of the O, N, S, and Se (Se 4 S 4 O 4 N), which plays also an important role in the charge transport and other physical properties. For instance, for some selected square-planar Ni-coordinated complexes (Fig.…”

“…8d), rather than the staggered AB (ABAB) mode. 46,48,50,51,54 Taking carefully in the AA symmetry, the AA-serrated (AA 0 AA 0 ) stacking (Fig. 8e), so called ''slipped-parallel AB stacking'' with slightly slipped arrangement in every two layers, 19,28,32,33,36,39,40,42,52,53,57,59,68,96,97,99 and AAinclined (AA 0 A 00 A 0 0 0 , that is, the layers are continuously shifted in one direction) stacking (Fig.…”