Chemical reactions were used to synthesize 2,11,20-tris(ethanedithia)-9,18,27-trimethoxy-6,15, 24-tri-tert-butyl[3.3.3]metacyclophane 2 and 2,11-bis(ethanedithia)-9,18,27-trimethoxy-6,15,24-tri-tert-butyl[3.3.3]metacy...Chemical reactions were used to synthesize 2,11,20-tris(ethanedithia)-9,18,27-trimethoxy-6,15, 24-tri-tert-butyl[3.3.3]metacyclophane 2 and 2,11-bis(ethanedithia)-9,18,27-trimethoxy-6,15,24-tri-tert-butyl[3.3.3]metacyclophane 4 from 6,15,24-tri-tert-butyl-9,18,27-trimethoxy[3.3.3]meta-cyclophane-2,11,20-trione 1 and -2,11-dione 3. The yields of 2 and 4 were 70% and 81% respectively. The conformations of the synthesized compounds 2 and 4 were studied using mainly solution Proton Nuclear Magnetic Resonance (1H NMR) spectroscopic methods. Compounds 2 and 4 were found to have a partial-cone conformation. Detailed variable temperature Proton Nuclear Magnetic Resonance studies further confirmed the partial-cone conformation for the two products, 2, 4. During the variable temperature nuclear magnetic resonance spectroscopic studies, compound 2 was found to have a coalescence temperature of about 0?C. Extraction of silver ions with compound 2 gave an extractability of 82% while the parent compound 1 showed zero (0) silver affinity. A 1:1 mol/mol mixture of compound 2 and silver ions studied by solution 1H NMR revealed a novel “Molecular Roulette” type of motion.展开更多
Two new macrocyclic compounds, [Cu2（L）2]（ClO4）4·2CH3OH （1） and [Cu（L）]（ClO4）2·2H2O （2） （L = 1,3,10,12,15,18-hexaazatetracyclodocosane） were synthesized by condensation reactions involving amine...Two new macrocyclic compounds, [Cu2（L）2]（ClO4）4·2CH3OH （1） and [Cu（L）]（ClO4）2·2H2O （2） （L = 1,3,10,12,15,18-hexaazatetracyclodocosane） were synthesized by condensation reactions involving amines and formaldehyde in the presence of copper anion. Compound 1 crystallizes in triclinic, space group Pí with a = 10.442（2）, b = 14.197（3）, c = 17.388（4）, α = 91.218（4）, β = 90.69（3）, γ = 93.756（4）o, V = 2520.4（9）3, Z = 2, F（000） = 1260, Dc = 1.589 Mg/m3, Mr = 1205.92, μ = 1.137 mm-1, λ = 0.71073, the final R = 0.0668 and wR = 0.1573 for 9703 observed reflections with I 2σ（I）. Compound 2 crystallizes in monoclinic, space group C2/c with a = 16.911（2）, b = 11.4172（15）, c = 27.059（4）, β = 107.787（2）o, V = 4974.7（12）3, Z = 8, F（000） = 2504, Dc = 1.610 Mg/m3, Mr = 602.92, μ = 1.155 mm-1, λ = 0.71073, the final R = 0.0419 and wR = 0.1131 for 4374 observed reflections with I 2σ（I）.展开更多
文摘Chemical reactions were used to synthesize 2,11,20-tris(ethanedithia)-9,18,27-trimethoxy-6,15, 24-tri-tert-butyl[3.3.3]metacyclophane 2 and 2,11-bis(ethanedithia)-9,18,27-trimethoxy-6,15,24-tri-tert-butyl[3.3.3]metacyclophane 4 from 6,15,24-tri-tert-butyl-9,18,27-trimethoxy[3.3.3]meta-cyclophane-2,11,20-trione 1 and -2,11-dione 3. The yields of 2 and 4 were 70% and 81% respectively. The conformations of the synthesized compounds 2 and 4 were studied using mainly solution Proton Nuclear Magnetic Resonance (1H NMR) spectroscopic methods. Compounds 2 and 4 were found to have a partial-cone conformation. Detailed variable temperature Proton Nuclear Magnetic Resonance studies further confirmed the partial-cone conformation for the two products, 2, 4. During the variable temperature nuclear magnetic resonance spectroscopic studies, compound 2 was found to have a coalescence temperature of about 0?C. Extraction of silver ions with compound 2 gave an extractability of 82% while the parent compound 1 showed zero (0) silver affinity. A 1:1 mol/mol mixture of compound 2 and silver ions studied by solution 1H NMR revealed a novel “Molecular Roulette” type of motion.
文摘Two new macrocyclic compounds, [Cu2（L）2]（ClO4）4·2CH3OH （1） and [Cu（L）]（ClO4）2·2H2O （2） （L = 1,3,10,12,15,18-hexaazatetracyclodocosane） were synthesized by condensation reactions involving amines and formaldehyde in the presence of copper anion. Compound 1 crystallizes in triclinic, space group Pí with a = 10.442（2）, b = 14.197（3）, c = 17.388（4）, α = 91.218（4）, β = 90.69（3）, γ = 93.756（4）o, V = 2520.4（9）3, Z = 2, F（000） = 1260, Dc = 1.589 Mg/m3, Mr = 1205.92, μ = 1.137 mm-1, λ = 0.71073, the final R = 0.0668 and wR = 0.1573 for 9703 observed reflections with I 2σ（I）. Compound 2 crystallizes in monoclinic, space group C2/c with a = 16.911（2）, b = 11.4172（15）, c = 27.059（4）, β = 107.787（2）o, V = 4974.7（12）3, Z = 8, F（000） = 2504, Dc = 1.610 Mg/m3, Mr = 602.92, μ = 1.155 mm-1, λ = 0.71073, the final R = 0.0419 and wR = 0.1131 for 4374 observed reflections with I 2σ（I）.
