Maji Tapas Kumar, Ohba Masaaki, Kitagawa Susumu
Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
Inorg Chem. 2005 Dec 12;44(25):9225-31. doi: 10.1021/ic050835g.
Two novel coordination polymers of Cu(II), viz. [Cu(bipy)(1,4-napdc)(H2O)2]n and {Cu(bpe)1.5(1,4-napdc)}n (bipy=4,4'-bipyridine; bpe=1,2-bis(4-pyridyl)ethane; 1,4-napdc2-=1,4-naphthalenedicarboxylate), have been synthesized and structurally characterized by changing only the pillar motifs. Both the compounds crystallize by slow evaporation from the ammoniacal solution of the as-synthesized solid. Framework 1 crystallizes in monoclinic crystal system, space group P2/n (No. 13), with a=11.028(19) A, b=11.16(3) A, c=7.678(13) A, beta=103.30(5) degrees, and Z=2. Framework 2 crystallizes in triclinic system, space group, P (No. 2), a=10.613(4) A, b=10.828(10) A, c=13.333(9) A, alpha=85.25(9) degrees, beta=82.59(6) degrees, gamma=60.37(5) degrees, and Z=2. The structure determination reveals that has a 2D network based on rectangular grids, where each Cu(II) is in 4+2 coordination mode. The 2D networks stacked in a staggered manner through the pi-pi interaction to form a 3D supramolecular network. In the case of, a {Cu(bpe)1.5}n ladder connected by 1,4-napdc2- results a 2D cuboidal bilayer network and each bilayer network is interlocked by two adjacent identical network (upper and lower) forming 3-fold interpenetrated 3D framework with small channel along the c-axis, which accommodates two water molecules. The TGA and XRPD measurements reveal that both the frameworks are stable after dehydration. Adsorption measurements (N2, CO2, and different solvents, like H2O, MeOH, etc.) were carried out for both frameworks. Framework shows type-II sorption profile with N2 in contrast to H2O and MeOH, which are chemisorbed in the framework. In case of, only H2O molecules can diffuse into the micropore, whereas N2, CO2, and MeOH cannot be adsorbed, as corroborated by the smaller channel aperture. The low-temperature (300-2 K) magnetic measurement of and reveals that both are weakly antiferromagnetically coupled (J=-1.85 cm-1, g=2.02; J=-0.153 cm-1, g=2.07), which is correlated by the magnetic pathway to the corresponding structure.
两种新型铜（II）配位聚合物，即[Cu(bipy)(1,4 - napdc)(H2O)2]n和{Cu(bpe)1.5(1,4 - napdc)}n（bipy = 4,4'-联吡啶；bpe = 1,2 - 双（4 - 吡啶基）乙烷；1,4 - napdc2- = 1,4 - 萘二甲酸根），已通过仅改变支柱基序进行了合成和结构表征。两种化合物均通过从合成固体的氨溶液中缓慢蒸发结晶得到。骨架1结晶于单斜晶系，空间群P2/n（编号13），a = 11.028(19) Å，b = 11.16(3) Å，c = 7.678(13) Å，β = 103.30(5)°，Z = 2。骨架2结晶于三斜晶系，空间群P（编号2），a = 10.613(4) Å，b = 10.828(10) Å，c = 13.333(9) Å，α = 85.25(9)°，β = 82.59(6)°，γ = 60.37(5)°，Z = 2。结构测定表明其具有基于矩形网格的二维网络，其中每个铜（II）处于4 + 2配位模式。二维网络通过π - π相互作用以交错方式堆叠形成三维超分子网络。在{Cu(bpe)1.5(1,4 - napdc)}n的情况下，由1,4 - napdc2-连接的{Cu(bpe)1.5}n梯子形成二维立方双层网络，并且每个双层网络由两个相邻的相同网络（上层和下层）互锁，形成沿c轴具有小通道且容纳两个水分子的三重互穿三维骨架。热重分析（TGA）和X射线粉末衍射（XRPD）测量表明两种骨架在脱水后均稳定。对两种骨架进行了吸附测量（N2、CO2以及不同溶剂，如H2O、MeOH等）。骨架1对N2显示出II型吸附曲线，与在骨架中化学吸附的H2O和MeOH形成对比。在{Cu(bpe)1.5(1,4 - napdc)}n的情况下，只有H2O分子能够扩散到微孔中，而N2、CO2和MeOH不能被吸附，较小的通道孔径证实了这一点。对[Cu(bipy)(1,4 - napdc)(H2O)2]n和{Cu(bpe)1.5(1,4 - napdc)}n的低温（300 - 2 K）磁性测量表明两者均为弱反铁磁耦合（J = -1.85 cm-1，g = 2.02；J = -0.153 cm-1，g = 2.07），这通过磁途径与相应结构相关。
