Five novel homochiral coordination polymers (HCPs) [Cu2(ODBALa)2(bpa)2H2O]·7H2O (1), [M(ODBALa)H2O]·H2O (M = Mn for 2; Co for 3), [Cu(ODBPRo)(bpe)]·7H2O (4) and [Cd2.5(ODBPRo)(HODBPRo)3(bpe)2.5]·13H2O (5) have been successfully synthesized by using designed chiral 4,4'-oxybisbenzoyl alanine/proline derivatives in the absence/presence of N-donor ancillary ligands, where H2ODBALa = 4,4'-oxybisbenzoyl-bis(l-alanine), H2ODBPRo = 4,4'-oxybisbenzoyl-bis(l-proline), bpa = 1,2-bis(4-pyridyl)ethane, and bpe = 1,2-bis(4-pyridyl)ethene. Interestingly, the combination of the chiral derivatives and metal ions gives various chiral metal-organic fragments, which are connected by N-donor ancillary ligands to construct the intriguing homochiral structures. In 1, 40-membered [Cu2(ODBALa)2] metallacycles as beads are strung by bpa ligands, yielding a one-dimension (1D) tortuous chain. Compounds 2 and 3 are isomorphous and possess a 3D metal-organic framework, embedding the unique (μ2-COO)(μ2-Ocarboxylate)(μ2-H2O) triple-bridges and twisted (-Mn4(ODBALa)4-)n left-handed helical chains. In 4, the [Cu(ODBPRo)]n left-handed helical chains are linked by bpe ligands to constitute a high undulated 2D layer. In 5, the crab-like [(Cd1)2(Cd2)(Cd3)2(HODBPRo)6(ODBPRo)2] fragments are joined together to form a 1D left-handed helical chain, which is further connected by bpe ligands to build a remarkable layered network. Magnetic susceptibility measurements of 2 and 3 indicate typical antiferromagnetic behaviour between the triple-bridging Mn(ii) ions in 2, whereas ferromagnetic coupling between the triple-bridging Co(ii) ions exists in 3. Moreover, the photoluminescent spectrum of 5 exhibits a strong solid-state emission at 414 nm.
Three novel, homochiral, porous metal–organic
frameworks based on the H2PDBAla ligand and different divalent
cations (Co(II)) and Cu(II)), namely, [M(PDBAla)(bipy)(H2O)2]·3H2O (M = Co 1 and Cu 2), [Cu(PDBAla)(bpea)]·7H2O (3) (H2PDBAla = pyridine-2,6-dicarbonyl-bis(l-alanine), bipy = 4,4′-bipyridine, bpea = 1,2-bis(4-pyridyl)ethane),
have been synthesized and characterized with the assistance of N-donor
ligands. The distinctive H2PDBAla ligands are coordinated
to divalent metal ions by the different coordination modes, forming
various helixes in compounds 1–3.
Compounds 1 and 2 are isostructural and
feature a 2-fold interpenetrating three-dimensional (3D) framework
with the cds topological net built by the combination
right-handed helical chains and bipy ligands, whereas a 3D framework
with the tcj topological net is observed in compound 3, wherein bpea ligands reinforce the 3D framework constructed
by right-handed helical chains. Compounds 1 and 3 display high CO2 absorption capability and superior
sorption enthalpies, reflecting the strong affinity of the frameworks
for CO2. Moreover, compound 3 exhibits a small
enantioselective separation performance for racemic alcohol.
Self-assembly of divalent metal ions and designed amino acid derivatives, 4,4′-biphenyl-bis[carbonyl-N-(alanine)] (H 2 BPBAla) and 4,4′-biphenylbis [carbonyl-N-(proline)] (H 2 BPBPro), as well as ancillary ligands, 1,2-bis(4pyridyl)ethane (bpea) and N,N′-bis(4-pyridyl)isophthalamide (bpipa), generated seven homochiral coordination polymers [Cu 2 (BPBAla) 7). All compounds contain different chiral metal-amino acid derivative helixes, which are tuned by varied conformation and configuration of N-donor ligands. 1 exhibits left-handed, doublestranded Cu-BPBAla helical chains tuned by the trans-conformation bpea ligand, whereas isostructural 2 and 3 exhibit right-handed, single-stranded Co/Ni-BPBAla helical chains tuned by the gauche-conformation bpea ligand. In the absence of an ancillary ligand, 4 displays a two-dimensional (2D) Cd-BPBAla layered network made up of left-handed, single-stranded (−Cd-O−) n helical chains and right-handed, double-stranded Cd-BPBPro-fragment helical chains. When H 2 BPBPro replaces H 2 BPBAla, 5 becomes a three-dimensional (3D) framework composed of right-handed, single-stranded Cu-BPBPro helical chains and transconformation bpea ligand. 6 and 7 are isostructural 3D frameworks and constructed by the coalition of left-handed, single-stranded Cd/Zn-BPBPro and Cd/Zn-bpipa helical chains, and there is an angle of 92.28°between the two Cd/Zn-BPBPro helical chains. The photoluminescence spectra of 4, 6, and 7 reveal the corresponding emission of ligands. More significantly, 6 and 7 can effectively detect the natural acidic amino acids by the enhancement of UV absorption intensity.
Eight new coordination compounds built by an unexplored semi-rigid ether-based unsymmetrical tetracarboxylate and varied dipyridyl ligands have been synthesized. Their variety of structures, photoluminescence and magnetic properties are discussed.
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