Hai-Yan Li

Tuning zinc(II) coordination polymers based on bis(1,2,4-triazol-1-yl)ethane and 5-substituted 1,3-benzenedicarboxylates: syntheses, structures and properties

In our effect to tune the structures of Zn(II) coordination polymers, six zinc(II) coordination polymers {[Zn(bte)(1,3-bdc)]·0.5H2O}n (1), {[Zn(bte)(NO2-1,3-bdc)]·3H2O}n (2), {[Zn(bte)(I-1,3-bdc)(H2O)]·H2O}n (3), {[Zn(bte)2(H2O)2](SO3-1,3-Hbdc)·4H2O}n (4), {[Zn(bte)(Hbtc)]·3H2O}n (5) and {[Zn3(bte)2(btc)2(H2O)2]·2.5H2O}n (6) (bte = 1,2-bis(1,2,4-triazol-1-yl)ethane, 1,3-bdc = 1,3-benzenedicarboxylate, NO2-bdc = 5-nitroisophthalate, I-1,3-bdc = 5-iodoisophthalate, SO3-1,3-bdc = 5-sulfoisophthalate, btc = 1,3,5-benzenetricarboxylate) have been synthesized and structurally characterized. 1, 2 and 3 are independent 1D MONTs. An interesting structural feature of 3 is that the I groups of each 1D MONT polythread into two adjacent 1D MONTs to form a (1D → 2D) polythreaded array and a 3D supramolecular architecture. 4 shows the double chain cation [Zn(bte)2(H2O)2]n2n+ and 3D hydrogen bond architecture. 5 exhibits a 2D (4,4) network and a 3D hydrogen bond architecture. In 6, each btc ligand bridges three Zn(II) atoms (one Zn1 and two Zn2) and forms a 3-connected 2D network [Zn3(btc)2(H2O)2]n. Each bte ligand connects two [Zn3(btc)2(H2O)2]n 2D networks to construct a (3,4)-connected 3D network with point symbol (62·144)(143)4. Such a (3,4)-connected 3D network is unprecedented, as to the best of our knowledge. The luminescence and thermal stability of 1–6 were investigated.

A polythreading coordination array formed from 2D grid networks and 1D chains

The reaction of ZnCl2 or Zn(NO3)2 with the flexible ligand 1,3-bis(1,2,4-triazol-1-yl)propane (btp) and 1,4-benzenedicarboxylate (1,4-bdc) affords two coordination polymers, in which 1 represents a new type of entanglement that only a half of the loops of 2D networks are polythreading by 1D chains containing alternating rings and rods, however, 2 has a special 2D (6,3) network, with six Zn(II) atoms at six corners and four 1,4-bdc and two double btp at six edges.

A polythreading coordination array formed from a 3D microporous cation network and 1D anion ladders

The reaction of btre with CdCl2 or a mixture of CdCl2 and Na[N(CN)2] affords two coordination polymers, in which 1 forms a 3D microporous cation network, however, 2 exhibits a polythreading coordination array formed from a 3D microporous cation network and 1D anion ladders.

Structurally versatile cadmium coordination polymers based on bis(1,2,4-triazol)ethane and rigid aromatic multicarboxylates: syntheses, structures and properties

Nine Cd(II) coordination polymers {[Cd(bte)(NO2-bdc)(H2O)]·H2O}n (1), {[Cd(bte)(I-bdc)(H2O)]·H2O}n (2), {[Cd(bte)0.5(OH-bdc)(H2O)]·H2O}n (3), {[Cd(bte)2(H2O)2]·(SO3-Hbdc)·4H2O}n (4), {[Cd(bte)0.5(1,4-bdc)(H2O)]·2H2O}n (5), {[Cd2(bte)2(btec)(H2O)2]·11H2O}n (6), [Cd(btre)(obc)2]n (7), {[Cd(btre)0.5(NO2-bdc)(H2O)2]·H2O}n (8) and {[Cd3(btre)2(SO3-bdc)2]·4H2O}n (9) (bte = 1,2-bis(1,2,4-triazol-1-yl)ethane, btre = 1,2-bis(1,2,4-triazol-4-yl)ethane, NO2-bdc = 5-nitroisophthalate, I-bdc = 5-iodoisophthalate, OH-bdc = 5-hydroxyisophthalate, SO3-bdc = 5-sulfoisophthalate, 1,4-bdc = 1,4-benzenedicarboxylate, btec = 1,2,4,5-benzenetetracarboxylate, obc = 4-hydroxybenzenecarboxylate) have been synthesized and structurally characterized. 1 and 2 are independent 1D MONTs. An interesting structural feature of 1 and 2 is that the NO2 or I groups of each 1D MONT polythread into two adjacent 1D MONTs to form a (1D → 2D) polythreaded array. 3 is a (3,4)-connected 2D network with the point symbol (42·6)(42·63·8). 4 shows the double chain cation [Cd(bte)2(H2O)2]n2n+ and 3D hydrogen bond architecture. The structure of 5 is an unusual (4,4)-connected 3D network with the point symbol (4·6·84)(4·63·82)2. 6 is an unusual (3,4)-connected 3D network with the point symbol (83)2(86). The structures of 7 and 8 are the 1D chain and 1D ladder, respectively. 9 exhibits an unusual (3,5,5,6)-connected three-dimensional network with the point symbol (42·8)2(43·83·103·12)2(43·6·83·103)2(44·63·86·102). The luminescence and thermal stability of 1–9 were investigated.

A polythreading array formed by a (3,5)-connected 3D anionic network and 1D cationic chains: synthesis, structure, and catalytic properties

An unusual copper(II) coordination polymer {[Cu(tmtz)(H2O)4][Cu2(tmtz)2(sip)2]·4H2O}n (1) (tmtz = 1,4-bis(1,2,4-triazol-1-ylmethyl)-2,3,4,5-tetramethylbenzene, sip = 5-sulfoisophthalate) is synthesized by the hydrothermal reaction. X-Ray structural analysis shows that 1 is comprised of two distinct and crystallographically independent polymeric motifs polythreading together. The first motif of 1 is an unusual (3,5)-connected 3D anionic network [Cu2(tmtz)2(sip)2]. The second motif in 1 is the [Cu(tmtz)(H2O)4]n 1D cationic chain. A polythreading array formed by a (3,5)-connected 3D anionic network and 1D cationic chains. The catalytic performance exhibits that 1 is active as a catalyst for the degradation of methyl orange. The thermal analysis is also observed.

Spacer length-controlled assembly of [CunIn]-based coordination polymers from CuI and bis(4-phenylpyrimidine-2-thio)alkane ligands

Reactions of CuI with bis(4-phenylpyrimidine-2-thio)alkane ligands with different spacer lengths, [(phpy)(CH2)n(phpy)] (phpyH = 4-phenylpyrimidine-2-thiol; n = 1, bphpym; n = 2, bphpye; n = 3, bphpypr; n = 4, bphpyb; n = 5, bphpyp; n = 6, bphpyh), afforded a set of six [CunIn]-based coordination polymers, [{Cu(μ3-I)}2(phpym)]n (1), [{Cu(μ3-I)}4(bphpye)]n (2), [{(MeCN)Cu3(μ-I)2(μ4-I)}2(bphpypr)2]n (3), [{((MeCN)Cu)(μ-I)}2(bphpyb)]n (4), [{Cu2(μ-I)(μ3-I)}2(bphpyp)2]n (5) and [{((MeCN)Cu)(μ3-I)}2{Cu(μ-I)}2(bphpyh)2]n (6), respectively. Compounds 1–6 were characterized by elemental analysis, IR and single-crystal X-ray crystallography. 1 and 2 consist of an unique 2D network in which the 1D staircase [Cu2I2]n chains are linked by phpym or phpye ligands via the μ-η1(N)-η1(N) or μ-η1(N),η1(S)-η1(N),η1(S) coordination modes, respectively. Complexes 3 and 5 consist of double butterfly-shaped {(MeCN)Cu3(μ-I)2(μ4-I)}2 units or chair-like [Cu2(μ-I)(μ3-I)]2 units that are linked to their neighboring ones by pairs of bphpypr or bphpyp bridges to form a 1D double chain. 4 contains a 1D zigzag chain assembled by dimeric [{(MeCN)Cu}(μ-I)]2 cores and bphpyb ligands. In 6, unique 1D tandem-rhomboid [Cu2I2]n chains are connected by dphpyh ligands to form a 2D staircase network. In addition, the photoluminescent properties of 1–6 in the solid state at ambient temperature were investigated.

Structural versatility of seven copper(II) coordination polymers constructed with the long flexible ligand 1,4-bis(1,2,4-triazol-1-yl)butane

The assembly reaction of 1,4-bis(1,2,4-triazol-1-yl)butane (btb) with different Cu(II) salts yields five coordination polymers: a 1D linear chain [Cu(btb)(HCOO)2(H2O)2]n (1), a 2D (4, 4) network [Cu(btb)2Cl2]n (2), a 3D cubic network [Cu(btb)(NCS)2]n (3), a threefold interpenetrating 3D diamondoid network {[Cu(btb)2(H2O)2](ClO4)2}n (4) and {[Cu(btb)2(H2O)2](NO3)2}n (5). 1 further constructs a 3D hydrogen bonding network. Two coordination polymers [Cu(btb)(1,2-bdc)]n (6) and {[Cu2(btb)(btec)(H2O)3]0.5H2O·CH3OH]n (7) were obtained with btb, 1,2-benzenedicarboxylate (1,2-bdc) and 1,2,4,5-benzenetetracarboxylate (btec). 6 is a 4-connected 65·8-CdS 3D coordination network. 7 is a (3,4,5)-connected pillared-layer 3D porous network where [Cu2(btb)(btec)(H2O)3] 2D layers are interlinked by btb pillars. The thermal stability of 1–7 was investigated. 3 and 6 are paramagnets with a negligible magnetic interaction while antiferromagnetic coupling between Cu(II) ions is observed in 7.

Seven structural versatile coordination polymers based on a flexible bis(triazole) and polycarboxylate co-ligands: syntheses, structures and properties

Seven coordination polymers {[Mn(tmtz)0.5(OH-bdc)(H2O)2]·2.75H2O}n (1), [Mn(tmtz)1.5(1,3-bdc)]n (2), [Mn(tmtz)(1,4-bdc)]n (3), [Co(tmtz)(oba]n (4), {[Co4(tmtz)2(bptc)2(H2O)7]·3.5H2O}n (5), {[Ni(tmtz)1.5(1,3-bdc)]·0.5H2O}n (6), [Ni(tmtz)(oba)(H2O)]n (7) (tmtz = 1,4-bis(1,2,4-triazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene, OH-bdc = 5-hydroxy-1,3-benzenedicarboxylate, 1,3-bdc = 1,3-benzenedicarboxylate, 1,4-bdc = 1,4-benzenedicarboxylate, H2oba = 4,4′-oxybis(benzoic acid), bptc = 3,3′,4,4′-benzophenonetetracarboxylate) have been synthesized and structurally characterized. 1 exhibits a 1D ladder structure and a 3D supramolecular architecture. 2 and 6 have similar 5-connected 2D networks through the 1,3-bdc ligand connecting [M(tmtz)1.5]n 1D ladders, with the point symbol (48·62). 3 has a (4,6)-connected 3D fsc network with a point symbol of (44·62)(44·610·8). 4 shows a 1D tubular-like chain. 5 exhibits a complicated (3,4,4)-connected 3D network with a point symbol of (4·10·12)2(4·83·10·12)2(82·102·122). Such a (3,4,4)-connected 3D network is unprecedented to the best of our knowledge. 7 displays a 2D (4,4) network which crystallizes in the chiral orthorhombic space group P212121. The results indicate that the central metal ions, polycarboxylate and flexible triazole co-ligands have a great effect on the formation and the structures of the coordination polymers. The thermal stability and luminescence were investigated. The crystal structures and solid-state circular dichroism (CD) spectra measurements confirmed the occurrence of the spontaneous resolution of 7 and demonstrated that the resulting crystal of 7 is a racemic mixture.

Cubane-type {M4O4} (M = CoII, ZnII, CuII) clusters: synthesis, crystal structures, and luminescent and magnetic properties

The employment of the hydroxyl-rich ligand (E)-3-((2-hydroxy-3-methoxybenzylidene)amino)propane-1,2-diol (H3L) in the chemistry of cubane-type {M4O4} clusters is reported. Three cubane-type clusters of the formula [M4(HL)4] (M = CoII (1), ZnII (2), CuII (3)) were achieved by reactions of metal acetates with H3L under solvothermal conditions. The structures of 1, 2 and 3 have been established by single-crystal X-ray diffraction studies. The tetranuclear clusters 1–3 have cubane-type [M4(μ3-OR)4]4+ cores with divalent metal atoms and deprotonated oxygen atoms (originating from the HL2− ligands) occupying alternate vertices. The luminescence studies suggest strong emission for 2 in the solid state at room temperature. The magnetic properties of 1 and 3 have been investigated. The variable-temperature dc magnetic susceptibility studies indicate ferromagnetic MII⋯MII exchange interactions for 1 and 3. The ac magnetic susceptibility investigation reveals that complex 1 shows slow magnetic relaxation (SMM) behavior.

An efficient approach to the ammoxidation of alcohols to nitriles and the aerobic oxidation of alcohols to aldehydes in water using Cu(II)/pypzacac complexes as catalysts

Reactions of 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)acetic acid (pypzacacH) ligand with Cu(OAc)2, Cu(NO3)2, CuSO4, Cu(ClO4)2 or CuCl2 produced four dinuclear Cu(II) complexes [{(MeOH)Cu(OAc)}(μ-κ2:κ1-pypzacac)]2·0.5H2O (1·0.5H2O), [{Cu(pypzacac)}(μ-κ2:κ1-pypzacac)2{Cu(H2O)2}](NO3)·2(MeOH)0.5·6H2O (2·2(MeOH)0.5·6H2O), [{(MeOH)Cu(mpypzacac)}(μ-SO4)]2·2MeOH (3·2MeOH; mpypzacac = methyl 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)acetate), [{Cu(mpypzacac)2}(μ-κ2:κ1-pypzacac){Cu(mpypzacac)}](ClO4)3·MeOH (4·MeOH) and one polymeric Cu(II) complex [(CuCl)(μ-κ3:κ1-pypzacac)]n (5), respectively. The mpypzacac ligand in 3 and 4 was in situ generated via the Cu2+-catalyzed dehydrative esterification of acetic acid of the pypzacacH ligand. Complexes 1–5 are characterized by elemental analysis, IR and single-crystal X-ray diffraction. Complex 1 contains two {(MeOH)Cu(OAc)} fragments that are interconnected by two μ-κ2:κ1-pypzacac− ligands, forming a dimeric structure. In 2, {Cu(pypzacac)} and {Cu(H2O)2} units are bridged by a pair of μ-κ2:κ1-pypzacac− ligands. In 3, two {Cu(mpypzacac)} fragments are linked by two μ-κ1:κ1-SO42− ions to form a dinuclear structure. Complex 4 also adopts a dimeric structure in which {Cu(mpypzacac)2} and {Cu(mpypzacac)} units are interconnected by one μ-κ3:κ1-pypzacac− ligand. Complex 5 contains a 1D chain in which (CuCl) fragments are interlinked by μ-κ3:κ1-pypzacac− ligands. Complexes 1–5 exhibited excellent catalytic performance in the ammoxidation of alcohol to nitrile and the aerobic oxidation of alcohol to aldehyde in water. The catalytic aqueous solution was easily separated and could be reused for several cycles without any obvious decay of catalytic efficiency.