MECHANISM OF THERMAL-DECOMPOSITION OF DINEOPENTYLBIS(TRIETHYLPHOSPHINE)PLATINUM(II) - FORMATION OF BIS(TRIETHYLPHOSPHINE)-3,3-DIMETHYLPLATINACYCLOBUTANE
MECHANISM OF THERMAL-DECOMPOSITION OF DINEOPENTYLBIS(TRIETHYLPHOSPHINE)PLATINUM(II) - FORMATION OF BIS(TRIETHYLPHOSPHINE)-3,3-DIMETHYLPLATINACYCLOBUTANE
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DOI：
10.1021/ja00542a009
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发表时间：
1980-01-01
影响因子：
15
通讯作者：
WHITESIDES, GM
中科院分区：
文献类型：
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作者：
FOLEY, P;DICOSIMO, R;WHITESIDES, GM
结论碘部分氧化金属酞菁化合物提供了一类广泛的新型分子导体。如在本例中所示的镍酞菁，所得到的固态阵列的阳离子自由基的性质包括导电性，这是最好的已知的堆叠的分子导体相媲美。NiPcII的一个特别有趣的特性。电荷传输是从金属到半导体行为的转变，其显然不反映在载流子的磁性中。人们很容易推测，这种行为反映了载流子迁移率的变化所带来的一些微妙的结构重排。从更广泛的角度来看，碘化金属酞菁，如这里报道的那些，代表了第一个进入基于混合价金属大环阵列的配体tt系统的导电材料的拓宽领域。显然，所收集的见解和开发的方法将导致对促进电荷传导和优化材料性能的分子特征的不断深入的理解。这项研究得到了NSF-MRL计划通过西北大学材料研究中心（授予DMR 76 - 80847 A01），NSF（授予BMH DMR 77 - 26409和授予JAI CHE 76 - 10335）和海军研究办公室（TJM）的慷慨支持。我们感谢J. B教授。Cohen先生协助进行漫散射测量，J. Martinsen先生协助进行静态磁化率测量。我们感谢斯坦利博士。红宝石的阿贡国家实验室物理部记录的碘穆斯堡尔谱的NiPc 129 I2。i6.
Conclusions Partial oxidation of metallophthalocyanines with iodine has provided an extensive new class of molecular conductors. As illustrated in the present case with nickel phthalocyanine, the properties of the resulting solid-state array of-cationradicals include electrical conductivity which is comparable with that of the best known stacked molecular conductors. A particularly intriguing feature of NiPcIi. o charge transport is a transition from metallic to semiconducting behavior which apparently is not re-flected in the magnetic properties of the carriers. It is tempting to speculate that this behavior reflects a change in carrier mobility brought about by some subtle structural rearrangement. In a broader perspective, the iodinated metallophthalocyanines, such as those reported here, represent the first entry into a wid-ening area of conductive materials based upon the ligand tt systems of mixed-valent metallomacrocyclicarrays. Clearly the insights gleaned and the methodology developed will lead to an ever-deepening understanding of those molecular characteristics which facilitate charge conduction and which optimize materials performance.Acknowledgments. This research was generously supported by the NSF-MRL program through the Materials Research Center of Northwestern University (Grant DMR76-80847A01), by the NSF (Grant DMR77-26409 to BMH and Grant CHE76-10335 to JAI), and by the Office of Naval Research (to TJM). We thank Professor J. B. Cohen for assistance with the diffuse scattering measurements and Mr. J. Martinsen for assistance in the static susceptibility measurements. We thank Dr. StanleyL. Ruby of the Physics Division of Argonne National Laboratory for recordingthe iodine Mossbauer spectrum of NiPc129I2. i6.