Biomedical subjects
Publications and source records attributed to Susumu Kitagawa.
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A three-dimensional coordination framework constructed with 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) diainon has been synthesized and structurally characterized. This open framework possessing a highly electron-rich surface has an optical sensing cavity for several aromatics with crystal-to-crystal transformation and strong accommodation, which are based on a charge-transfer interaction with them.
Integration of mononuclear [Cr(CN)6]3- and preorganized trinuclear [Co2Ln(L)2]3+ complexes provides novel trimetallic magnets having a 3-D pillared-layer framework with an alternate array of 2-D layer extended by Cr(III)-CN-Co(II) linkages and Ln(III) ion. The overall magnetic nature can be systematically controlled by Ln(III) ions inserted between the 2-D ferromagnetic layers.
Three new coordination polymers, [CoCl2(4-pmna)2]n (1), {[Co(NCS)2(4-pmna)2].2Me2CO}n (2 superset 2Me2CO), and {[Co(4-pmna)2(H2O)2](NO3)2.2CH3OH}n (3 superset 2H2O.2MeOH) (4-pmna = N-(pyridin-4-ylmethyl)nicotinamide), have been synthesized and characterized using single-crystal X-ray diffraction. The cobalt(II) atoms are bridged by 4-pmna ligands in all three compounds to form double-stranded one-dimensional "repeated rhomboid-type" chains with rectangular-shaped cavities. In 1, each chain slips and obstructs the neighboring cavities so that there are no guest-incorporated pores. Both 2 superset 2Me2CO and 3 superset 2H2O.2MeOH do not have such a staggered arrangement and have pores that can be filled with a guest molecule. Compound 3 superset 2H2O.2MeOH traps guest molecules with multiple hydrogen bonds and shows a reversible structural rearrangement during adsorption and desorption. The new crystalline compound, 3, is stabilized by forming hydrogen bonds with the amide moieties of the 4-pmna ligands and was characterized using infrared spectroscopy. The clathration enthalpy of the reaction 3 + 2H2O(l) + 2MeOH(l) <==> 3 superset 2H2O.2MeOH (approximately 35 kJ/mol) was estimated from differential scanning calorimetry data by considering the vaporization enthalpies of H2O and MeOH. The desorption process of 3 superset 2H2O.2MeOH --> 3 follows a single zero-order reaction mechanism under isothermal conditions. The activation energy of ca. 100 kJ/mol was obtained by plotting the logarithm of the reaction time for the same reacted fraction versus the reciprocal of the temperature. Moreover, the distribution of the one-dimensional channels in 3 superset 2H2O.2MeOH was estimated using the observation that the reaction rate is directly proportional to the total sectional area.
This paper reports a novel crystal growth system of a coordination framework {[Cu3(CN)3{hat-(CN)3(OEt)3}]}n (1) (hat-(CN)3(OEt)3 = 2,6,10-tricyano-3,7,11-triethoxy-1,4,5,8,9,12-hexaazatriphenylene). The coordination polymer is crystallized through the reaction of 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (hat-(CN)6), ethanol, and copper(I) complex, involving the breaking and forming of covalent bonds. The crystal morphologies obtained in the present system contain dumbbells, cogwheels, and superlattices. Moreover, in the growth perpendicular to the c-axis, periodic ramification at regular interval is observed, affording superlattice morphologies. Observation of the growth of dumbbell crystals shows that the growth rates parallel and perpendicular to the crystallographic c-axis are quite different: the former shows a drastic change with the reaction duration, while the latter is almost constant. These results are reproduced as a simple reaction-diffusion system, indicating that chemical reactions on crystal surfaces play an important role in determining the macroscopic crystal morphologies.
A series of guest-binding Cu(II) coordination polymers, {[Cu(bpetha)2(acetone)2].2PF6}n (bpetha = 1,2-bis(4-pyridyl)ethane) (1), {[Cu(bpetha)2(DMF)2].2PF6}n (2), {[Cu(bpetha)(2)(MeCN)(2)].2PF6.2MeCN}n (3), {[Cu(bpetha)2(H2O)2].2PF6.3THF.2H2O}n (4), {[Cu(bpetha)2(H2O)2].2PF6.3dioxane}n (5), and {[Cu(bpetha)2(H2O)2].2PF6.2-PrOH.2H2O}n (6), have been synthesized and crystallographically characterized. Their framework stabilities and guest-exchange properties have also been investigated. All compounds form a similar framework motif, a "double chain", in which the bpetha ligands bridge Cu(II) centers to form 1-D [Cu(bpetha)2]n double chains. A variety of Lewis base guest molecules, such as H2O, acetone, DMF, MeCN, THF, dioxane, and 2-PrOH, are incorporated into the assembly of the 1-D double chains. These chains flexibly change their forms of assembly in a guest-dependent manner. Interestingly, acetone, DMF, and MeCN guests with a carbonyl or cyanide group coordinate directly to the axial sites of the Cu(II) centers; in contrast, THF, dioxane, and 2-PrOH guests with an ether or alcohol group are incorporated into the frameworks not via coordination bonds but via weak interactions (hydrogen bonds and van der Waals forces). This selectivity is probably due to steric effects at coordinated oxygen or nitrogen atoms of the guests. Crystal-to-crystal transformations triggered by guests are observed, during which guests coordinated to the Cu(II) axial sites are readily removed and replaced by other guests.
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Ni(II) coordination polymers with a 4,4'-azobis(pyridine) (azpy) ligand, {[Ni2(NCX)4(azpy)4].G}n (X = S, G (guest molecule) = MeOH (1.MeOH); X = S, G = EtOH (1.EtOH); X = S, G = H2O (1.H2O); X = S, G = no guest (1); X = Se, G = MeOH (2.MeOH); X = Se, G = H2O (2.H2O); X = Se, G = no guest (2)), have been synthesized and structurally characterized with their porosity. These compounds have one-dimensional periodic ultramicropores that contain the small guest molecules, H2O, MeOH, or EtOH, whose hydroxy groups interact with the S or Se atoms of isothiocyanate or isoselenocyanate, respectively, via -S(Se)...HO- hydrogen bonds. Although the molecular dimensions of the MeOH guest are considerably larger than the window size of the ultramicropore, 1.MeOH and 2.MeOH easily release their guest molecules without decomposition of the framework to form 1 and 2 without any guest molecules. This shows that 1 and 2 have dynamic ultramicropores constructed from the interpenetrating framework. The guest desorption experiments using 1.MeOH and 1.EtOH reveal that the difference in the desorption behavior is due to van der Waals interactions that depend on the molecular shape of the guest molecule in the ultramicropores and/or an entrance blocking effect that depends on the minimum dimensions of the guest molecule for the pore windows. A marked difference in the N2 and CH4 adsorption isotherms was observed and is associated with the strength of the host-guest interaction.
The combination of Ni2+, dipropylenetriamine (dipn), and [Cr(CN)6]3- affords the cyanide-bridged bimetallic assembly, [Ni(dipn)]3[Cr(CN)6]2.3H2O (1). This compound crystallizes in cubic space group Pa, with a = b = c = 20.9742(7) A and Z = 8. A three-dimensional network is constructed on the basis of a Cr8Ni12 cubane unit formed by an alternate array of [Cr(CN)6]3- and [Ni(dipn)]2+ units through Cr-CN-Ni-NC-Cr edges. Cryomagnetic studies reveal a ferromagnetic interaction between Cr(III) and Ni(II) ions and a long-range ferromagnetic ordering below 42 K with very small coercive field. To the best of our knowledge, this compound is the first "complete ferromagnet" providing three-dimensional ferromagnetic interaction through a three-dimensional bridging structure that is based on a cubic unit among general metal-oxide and molecule-based magnets. Magnetooptical studies demonstrate a strong correlation between magnetic and optical properties.
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Reversible vapochromic behavior of a porous copper(II) coordination polymer {[Cu(bhnq)(THF)2](THF)}n (1; THF = tetrahydrofuran) constructed from a flexible hingelike ligand H2bhnq [2,2'-bis(3-hydroxy-1,4-naphthoquinone)] has been investigated by adsorption measurements. The isotherms show large hysteretic and stepwise profiles, suggesting the occurrence of the guest-induced framework transformation. The dynamic coil-like behavior of 1 can be controlled through the change of the hydrogen-bonding interactions caused by the reversible and selective incorporation of guest molecules.
Chemical oxidation of [Ru2(6+)(3,6-DTBCat)4]2- affords [n-Bu4N][Ru2(3,6-DTBDiox)4].acetone (2.acetone). The oxidized species was characterized by X-ray crystallographic analysis and EPR, and the delocalization of the unpaired electron over the entire molecule was indicated. This example showed that the utilization of redox-active ligands into a Ru2 complex expanded the degree of freedom in the electronic structure. DFT calculations support this view, and the spin population was estimated to be approximately 18% and 82% for the Ru2 core and the four dioxolene ligands, respectively.
A porous coordination polymer (PCP) with immobilization of sodium cations on the pore surface has been synthesized, by employing a bifunctional carboxylate/sulfonate ligand, and structurally characterized. The porous framework with 1D channels of the dimension of 4.9 x 4.9 A2 shows high thermal stability ( approximately 330 degrees C), affording Type I adsorption isotherms for CO2, acetone, and benzene. The chemical shift of 13C NMR and characteristic adsorption energy (betaE0) of acetone adsorbed in this compound represent the Lewis acidity of this framework.
A series of sandwich-shaped complexes based on two square tetranuclear Ag(I) metallomacrocycles, [[Ag4(pprd)4]2(XF6)]-(BF4)6.8MeNO2 (pprd = 4-(2-pyridyl)pyrimidine; X = Si, Ge and Sn), in which a XF6(2-) anion is encapsulated, were prepared and their structures were characterized both in the solid state and solution.