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±¾ÈËÓ¢ÓïˮƽÓÐÏÞ£¬²»ÊǺÜÃ÷°×ÏÂÃæ¶ÎÂäÊÇʲôÒâ˼£¬ÍûÄÄλ°ïæ·ÒëÏ£¬Ð»Ð»£¡ Theoretical calculations performed by Honeybourne on closed-shell conjugated macrocyclic ligands placed in perfectly linear columnar stacks, with an interplanar spacing of 0.373 nm, pointed out that both metal-free phthalocyanines£¨ÌªÝ¼£© and hemiporphyrazines£¨°ë×ϲËຣ©,because of the large bandgaps, must show low ¨® values at room temperature when undoped, i.e., they will not act as intrinsic semiconductors. However, these results are extremely distance-dependent, and narrower bandgaps and larger bandwidths could be obtained by reducing the interplanar distance. Moreover, by taking into account the fact that the conductivity of the macrocycles is usually very low until donor-acceptor interactions occur, the studies were extended to open-shell (radical ions) systems. The calculations for two spacing distances (0.373 and 0.332 nm) showed that the metal-free phthalocyanine displays larger bandwidths and narrower bandgaps than the corresponding hemiporphyrazines£¨°ë×ϲËຣ©. Indeed, the H2Thp radical anion does not have at 0.373 nm the minimum bandwidth required to ensure enough mobility of the charge carriers. |
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°®ÓëÓêÏÂ: ½ð±Ò+1 2012-03-26 21:55:50
cybusun: ½ð±Ò+25, ·ÒëEPI+1, ¡ïÓаïÖú 2012-03-27 08:52:33
°®ÓëÓêÏÂ: ½ð±Ò+1 2012-03-26 21:55:50
cybusun: ½ð±Ò+25, ·ÒëEPI+1, ¡ïÓаïÖú 2012-03-27 08:52:33
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Honeybourne½øÐÐÀíÂÛ¼ÆËãÖ¸³ö£¬±Õ»·´ó»·¹²éîÅäÌåºÜºÃµÄǶÔÚÏßÐÔÖù×´¶Ñµþ£¨Ò»ÖÖ¾§°û¶Ñµþ·½Ê½£¿£©£¬Ãæ¼ä¾àÊÇ0.373ÄÉÃ×£»ÎÞ½ðÊôÅä»ùµÄ̪ݼºÍ°ë×ϲËຣ¬ÓÉÓÚËüÃǾßÓдóµÄÄÜ´øÏ¶£¬ÔÚÎÞ²ôÔÓµÄÇé¿öϱØÈ»±íÏÖ³öµÍÅ·Ä·Öµ£¬Ò²¾ÍÊÇ˵ËüÃDz»»á³äµ±¾«Ãܵİ뵼Ì塣Ȼ¶ø£¬ÕâЩ½á¹û¶¼ÊǼ«ÆäÒÀÀµ¾àÀëµÄ£¬Í¨¹ý¼õС¾§Ãæ¾à¿ÉÒÔ»ñµÃÕÄÜ´øÏ¶ºÍ´óµÄƵ¿í¡£´ËÍ⣬¿¼Âǵ½µÄ´ó»·»¯ºÏÎïµÄµçµ¼ÂÊͨ³£ÊǷdz£µÍµÄ£¬³ý·ÇÌå - ÊÜÌå·¢ÉúÏ໥×÷Óã¬Ñо¿À©´ó×ÔÓÉ»ùÀë×Óϵͳ¡£ Á½¸ö¾§Ãæ¾àÀ루0.373ºÍ0.332 nm£©µÄ¼ÆËã±íÃ÷£¬ÎÞ½ðÊô̪ݼ£¨±ÈÏàÓ¦µÄhemiporphyrazines°ë×ϲËຣ©ÏÔʾ¸ü´óµÄ´ø¿íºÍÕÄÜ϶¡£ÊÂʵÉÏ£¬H2ThpµÄÒõÀë×Ó×ÔÓÉ»ùûÓÐÔÚ0.373ÄÉÃ×ËùÐèµÄ×îСƵ¿í£¬ÒÔÈ·±£µçºÉÔØÌå×ã¹»µÄÁ÷¶¯ÐÔ¡£ |

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