Three-dimensional homochiral manganese–lanthanide frameworks based on chiral camphorates with multi-coordination modes

Abstract

A series of 3D homochiral manganese-lanthanide frameworks have been synthesized based on chiral camphoric acid. In the heterometallic features, D-camphoric acids are unprecedentedly embedded in three coordination modes.

Metal–Organic Frameworks Constructed from d-Camphor Acid: Bifunctional Properties Related to Luminescence Sensing and Liquid-Phase Separation

“…As illustrated in Figure 1a 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 which are close to those reported for mangnese (II) complexes with D-cam 2and N-donor auxiliary ligands. 40 The single two-dimensional (2D) layer for compound 1 is accomplished by D-cam 2and bimb interlinking the metal centers ( Figure S1a). Apparently, the Mn(II) centers were viewed as four-connectors bridging two D-cam 2moieties and two bimb linkers, and thus the topology 41-42 of 1 is a 4-connected sql net with its point (Schläfli) symbol of (4 4 ·6 2 ).…”

Chiral Lanthanide Metal-Organic Frameworks

“…Dang et al [59] synthesized four 3D isostructural homochiral manganeselanthanide frameworks {MnLn(D-cam) 2 [56] by permission of The Royal Society of Chemistry. Reproduced from Sun et al [57] by permission of The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC) Chiral Lanthanide Metal-Organic Frameworks structure.…”

A Nonlinear Optically Active Bismuth–Camphorate Coordination Polymer

“…A well‐known strategy for engineering chiral CPs consists of using chiral ligands, whose “push‐pull” effect becomes cumulative through the multiple coordination to metal centers . In that respect, camphoric acid (or 1,2,2‐trimethylcyclopentane‐1,3‐dicarboxylic acid) seems to be a good candidate to be used as organic spacer for synthesis of CPs since it presents: (i) two complexing carboxylate groups, able to coordinate cations and form multidimensional CPs, as it has been already proven, aiming the preparation of multidimensional organic–inorganic hybrid materials; (ii) conformational rigidity due to the presence of five‐membered aliphatic ring; (iii) a relative low‐cost (produced by oxidizing the naturally occurring camphor with nitric acid), envisaging large scale synthetic approaches; (iv) an environmentally friendly character, with potential therapeutic effects (antiseptic, osteoblastic differentiation, antitumor); and (v) a chiral nature, essential to build up noncentrosymmetric materials.…”