| ²é¿´: 555 | »Ø¸´: 2 | |||
´óËÄдÂÛÎÄ½ð³æ (ÕýʽдÊÖ)
|
[ÇóÖú]
Çó·ÒëÕâ¶Î»°
|
|
Our attempts at targeted design of networks started with the choice of suitable building units and a coupling reaction with an effective catalyst. Figure 1 summarizes general aspects of our design: D4R cages with haloaryl terminal groups are versatile, highly connectable units for formation of inorganic¨Corganic hybrid polymers by means of well-developed cross-coupling reactions, for example, Heck reaction,Suzuki coupling, and Sonogashira coupling. Compound BrPh-D4R was chosen because it can be synthesized on a practical scale with high regio- and stereoselectivity by state-of-the-art cross-metathesis. As D4R cages resemble the secondary building units of several crystalline zeolite frameworks, linker molecules were selected by considering the default three-periodic nets that have practically been used to design crystalline framework materials including COFs. As mentioned above, however, it is nearly impossible to achieve polymer networks with long-range order, since most of them are formed under kinetic control. As a result, the three-periodic nets serve as merely qualitative guides to ideal structures. Three zeolite topologies (ACO,AFY, and LTA) can be built from D4R cages as the sole secondary building units. In their frameworks, the D4R cages are connected through two-coordinate linear linkers;the only difference is the orientation of the D4R cages. Considering the periodic arrangement of the discrete cages in such frameworks, the maximum symmetry of the ACO topology can be constructed from 1808 linear linkers without the need to rotate the D4R cages, and thus ACO appears to be the default topology. Accordingly, one can expect connection of the D4R cages with rigid, linear molecules (e.g.,1 and 2) to lead networks with local ACO-like structure ¡£ |
» ²ÂÄãϲ»¶
332Çóµ÷¼Á
ÒѾÓÐ5È˻ظ´
085701Çóµ÷¼Á³õÊÔ286·Ö
ÒѾÓÐ3È˻ظ´
²ÄÁϹ¤³Ì294Çóµ÷¼Á
ÒѾÓÐ4È˻ظ´
±¾¿ÆÐÂÄÜÔ´¿ÆÑ§Ó빤³Ì£¬Ò»Ö¾Ô¸»ªÀíÄܶ¯285Çóµ÷¼Á
ÒѾÓÐ10È˻ظ´
070305¸ß·Ö×Ó»¯Ñ§ÓëÎïÀí 304·ÖÇóµ÷¼Á
ÒѾÓÐ5È˻ظ´
083000ѧ˶274Çóµ÷¼Á
ÒѾÓÐ8È˻ظ´
Ò»Ö¾Ô¸±±¾©»¯¹¤´óѧ²ÄÁÏÓ뻯¹¤£¨085600£©296Çóµ÷¼Á
ÒѾÓÐ10È˻ظ´
Çóµ÷¼ÁÒ»Ö¾Ô¸º£´ó£¬0703»¯Ñ§Ñ§Ë¶304·Ö£¬Óдó´´ÏîÄ¿£¬Ëļ¶Òѹý
ÒѾÓÐ11È˻ظ´
071000ÉúÎïѧÇóµ÷¼Á£¬³õÊԳɼ¨343
ÒѾÓÐ7È˻ظ´
0703»¯Ñ§µ÷¼Á£¬Çóµ¼Ê¦ÊÕ
ÒѾÓÐ8È˻ظ´
qsdxueyuan
ͳæ (ÕýʽдÊÖ)
- Ó¦Öú: 8 (Ó×¶ùÔ°)
- ½ð±Ò: 566.9
- É¢½ð: 2391
- ºì»¨: 8
- Ìû×Ó: 481
- ÔÚÏß: 72.9Сʱ
- ³æºÅ: 3009230
- ×¢²á: 2014-03-02
- ÐÔ±ð: GG
- רҵ: ÈÈÁ¦Ñ§
¡¾´ð°¸¡¿Ó¦Öú»ØÌû
¡ï ¡ï ¡ï ¡ï ¡ï ¡ï ¡ï ¡ï ¡ï ¡ï ¡ï ¡ï ¡ï ¡ï ¡ï ¡ï ¡ï ¡ï ¡ï ¡ï ¡ï ¡ï ¡ï ¡ï ¡ï
´óËÄдÂÛÎÄ: ½ð±Ò+25, ¡ïÓаïÖú 2015-03-23 12:06:35
´óËÄдÂÛÎÄ: ½ð±Ò+25, ¡ïÓаïÖú 2015-03-23 12:06:35
|
ÎÒÃÇÊÔͼÔÚÍøÂçÓÐÕë¶ÔÐÔµÄÉè¼Æ¿ªÊ¼ÓëºÏÊʵĽ¨Öþµ¥Î»µÄÑ¡ÔñºÍÒ»¸öÓÐЧµÄ´ß»¯¼ÁµÄżÁª·´Ó¦¡£Í¼1×ܽáÁËÎÒÃǵÄÉè¼Æ¸Å¿ö£ºD4RÁý±´ú·¼»ù»ùÍÅ¿ÉÁ¬½Óµ¥ÔªµÄ¶à¹¦ÄÜ£¬¸ß¶È·¢´ïµÄ½»²æÅ¼Áª·´Ó¦£¬ÐγÉÎÞ»úÓлúÔÓ»¯¾ÛºÏÎïÀýÈç¨C£¬Heck·´Ó¦ºÍSonogashirażÁª£¬ÁåľżÁª¡£»¯ºÏÎïbrph-d4r±»Ñ¡ÖÐÊÇÒòΪËü¿ÉÒÔºÏ³É ÔÚ¸ßÇøÓòºÍÁ¢ÌåÑ¡ÔñÐÔµÄʵ¼Ê¹æÄ£×îÏȽøµÄ½»²æ¸´·Ö½â·´Ó¦¡£×÷ΪÏñ¼¸¸ö½á¾§·ÐʯD4RÁý¿ò¼ÜµÄ´Î¼¶½á¹¹µ¥Ôª£¬Á¬½Ó·Ö×ÓÓÉĬÈϵÄÈýÖÜÆÚµÄÓæÍø£¬¼¸ºõÒѾ±»ÓÃÀ´Éè¼Æ½á¾§¹Ç¼Ü²ÄÁϰüÀ¨½ØÖ¹ÆµÂÊÑ¡Ôñ¡£ÈçÉÏËùÊö£¬È»¶ø£¬Ëü¾ßÓг¤³ÌÓÐÐòʵÏÖ¾ÛºÏÎïÍøÂ缸ºõÊDz»¿ÉÄܵģ¬ÒòΪËûÃÇ´ó¶àÊǶ¯Á¦Ñ§¿ØÖÆÏÂÐγɵġ£×÷Ϊһ¸ö½á¹û£¬ÈýÖÜÆÚÍø×÷ΪֻÓж¨ÐÔÖ¸µ¼µÄÀíÏë½á¹¹¡£Èý·Ðʯ½á¹¹£¨ACO£¬ì³£¬LTA£©¿ÉÓÉD4RÁý×÷ΪΨһµÄ ´Î¼¶½á¹¹µ¥Ôª¡£ÔÚËûÃǵĿò¼Ü£¬D4RÁý×ÓÊÇͨ¹ýÁ½×ø±êÏßÐÔÁ¬½Ó£»Î¨Ò»µÄÇø±ðÊÇD4RÁý¶¨Î»¡£¿¼Âǵ½ÕâÑùÒ»¸ö¿ò¼ÜµÄÀëÉ¢ÖÜÆÚÐÔÅÅÁеÄÁý×Ó£¬ACOÍØÆË×î´óµÄ¶Ô³ÆÐÔ¿ÉÒÔÓÉ1808ÏßÐÔÁ¬½Ó¶ø²»ÐèҪת¶¯D4RÁý£¬Òò´ËËÆºõÊÇĬÈϵÄÍØÆËËã·¨¡£Òò´Ë£¬ÈËÃÇ¿ÉÒÔÆÚ´ýµÄD4RÁý¸ÕÐÔÁ¬½Ó£¬ÏßÐÔ·Ö×Ó£¨ÀýÈ磬1ºÍ2£©µ¼ÖÂÍøÂçµÄ¾Ö²¿Ëã·¨½á¹¹¡£ -------À´×Ô°Ù¶È·Òë¡£´óËÄÂÛÎÄÒªÇ󲻸ߣ¬Ó÷ÒëÈí¼þ¹È¸è»ò°Ù¶È·Òë³õ²½·Ò룬Ȼºó×Ô¼ºÕûºÏÓÃ×Ô¼ºµÄ»°±í´ï³öÀ´¾ÍÐУ¬×¢ÒâרҵÊõÓïµÄʹÓã¡£¡£¡ |

2Â¥2015-03-23 10:04:27
Î人һÐÄÒ»Òë
¾èÖú¹ó±ö (ÖøÃûдÊÖ)
- ·ÒëEPI: 502
- Ó¦Öú: 8 (Ó×¶ùÔ°)
- ½ð±Ò: 2283.1
- É¢½ð: 5914
- ºì»¨: 32
- Ìû×Ó: 1665
- ÔÚÏß: 321.9Сʱ
- ³æºÅ: 3587652
- ×¢²á: 2014-12-10
- ÐÔ±ð: GG
- רҵ: ¸ß·Ö×Ӻϳɻ¯Ñ§
¡¾´ð°¸¡¿Ó¦Öú»ØÌû
É̼ÒÒѾÖ÷¶¯ÉùÃ÷´Ë»ØÌû¿ÉÄܺ¬ÓÐÐû´«ÄÚÈÝ|
Our attempts at targeted design of networks started with the choice of suitable building units and a coupling reaction with an effective catalyst. ÎÒÃÇÊÔͼ¶Ô¾ÛºÏÎïÍøÂç½øÐÐÌØ¶¨Éè¼Æ£¬Ê×ÏÈÎÒÃǵÃÑ¡ÔñºÏÊʵĽ¨Ôìµ¥Ôª£¬ÒÔ¼°¾ßÓиßЧ´ß»¯¼ÁµÄñîºÏ·´Ó¦¡£ Figure 1 summarizes general aspects of our design: D4R cages with haloaryl terminal groups are versatile, highly connectable units for formation of inorganic¨Corganic hybrid polymers by means of well-developed cross-coupling reactions, for example, Heck reaction,Suzuki coupling, and Sonogashira coupling. ͼһ×ܽáÁËÎÒÃÇÉè¼ÆµÄ×ÛºÏÃæÏò£ºÒÔhaloaryl»ùÍÅΪÖն˵ÄD4RÁý·Ö×ÓÊÇÍòÄܵģ¬ËüÃǾßÓи߶ȿÉÁ¬½Óµ¥Ôª£¬Í¨¹ý³ÉÊìµÄñîºÏ·´Ó¦£¨ÀýÈ磺ºÕ¿Ë·´Ó¦£¬ÁåľñîºÏ·´Ó¦£¬ºÍËQͷżºÏ·´Ó¦ £©£¬ºÏ³ÉÓлú-ÎÞ»úÔÓ»¯¾ÛºÏÎï¡£ Compound BrPh-D4R was chosen because it can be synthesized on a practical scale with high regio- and stereoselectivity by state-of-the-art cross-metathesis. As D4R cages resemble the secondary building units of several crystalline zeolite frameworks, linker molecules were selected by considering the default three-periodic nets that have practically been used to design crystalline framework materials including COFs. ÎÒÃÇÖ®ËùÒÔ»áÑ¡ÔñBrPh-D4R£¬ÊÇÒòΪ£¬Í¨¹ý×îÏȽøµÄ¸´·Ö½â·´Ó¦£¬Ëü¿ÉÒÔÔÚ¸ßÇøºÍ¸ßÁ¢ÌåÑ¡ÔñÐÔµÄʵ¼ÊÌõ¼þϱ»ºÏ³É¡£ÓÉÓÚD4RÁý·Ö×ÓÓëÓÐЩ½á¾§Ë®¾§¿ò¼Ü½á¹¹ÀàËÆ£¬¿¼Âǵ½Ä¬ÈϵÄÈýÖÜÆÚ¾ÛºÏÎïÍøÂçÔÚʵ¼ÊÖÐÒѾ±»ÓÃÀ´ÖÆ×÷°üÀ¨ÏñCOFsµÄË®¾§¿ò¼Ü²ÄÁÏ£¬ËùÒÔÎÒÃÇÑ¡ÔñÁËÁ¬½Ó·Ö×Ó¡£ As mentioned above, however, it is nearly impossible to achieve polymer networks with long-range order, since most of them are formed under kinetic control. As a result, the three-periodic nets serve as merely qualitative guides to ideal structures. Three zeolite topologies (ACO,AFY, and LTA) can be built from D4R cages as the sole secondary building units. In their frameworks, the D4R cages are connected through two-coordinate linear linkers;the only difference is the orientation of the D4R cages. È»ºó£¬ÈçÉÏÎÄËù˵£¬ÒªÖÆ×÷³¤³ÌÓÐÐòµÄ¾ÛºÏÎïÍøÂ缸ºõÊDz»¿ÉÄܵģ¬ÒòΪÕâÖÖ³¤³ÌÓÐÐòµÄ¾ÛºÏÎïÍøÂç´ó¶àÊýÊÇÔÚ¶¯Á¦Ñ§¿ØÖÆÐγɵġ£Òò´Ë£¬ÈýÖÜÆÚ¾ÛºÏÎïÍøÂçÔÚÕâÀï½ö½ö×÷ΪһÖÖ¶¨ÐÔµÄÏòµ¼ÎïÖÊ£¬ÊǺϳÉÎï½á¹¹ÏëÀíÏëµÄ·½Ïò·¢Õ¹¡£ÒÔD4RÁý·Ö×Ó×÷ΪΨһµÄµÚ¶þµÈ½¨Ôìµ¥Ôª£¬¿ÉÒÔ½¨Á¢ÈýÖÓ·ÐÊ¯ÍØÆË(ACO,AFY,ºÍ LTA)¡£ÔÚÕâÐ©ÍØÆË½á¹¹ÖУ¬D4RÁý·Ö×ÓÊÇͨ¹ý¶þÅäλÏßÐÔÁ´½ÓÁ¬½ÓÆðÀ´£¬ËüÃÇÖ®¼äΨһ²»Í¬µÄÊÇD4RÁý·Ö×Ó³¯Ïò²»Í¬¡£ Considering the periodic arrangement of the discrete cages in such frameworks, the maximum symmetry of the ACO topology can be constructed from 1808 linear linkers without the need to rotate the D4R cages, and thus ACO appears to be the default topology. Accordingly, one can expect connection of the D4R cages with rigid, linear molecules (e.g.,1 and 2) to lead networks with local ACO-like structure ¼øÓÚÕâЩ½á¹¹ÖУ¬ÀëÉ¢µÄÁý·Ö×ÓµÄÖÜÆÚÐÔÅÅÁУ¬ÎÒÃÇ¿Éͨ¹ý1808ÏßÐÔÁ¬½Ó£¬ÎÞÐèÐýתD4RÁý·Ö×ӵij¯Ïò£¬´Ó¶øÊµÏÖACOÍØÆË×î´ó¶Ô³Æ£¬Òò´Ë£¬ACOÍØÆË×ÔÈ»³ÉÁËĬÈÏÍØÆËÁË¡£Óë´Ë¶ÔÓ¦£¬ÎÒÃÇ´ó¿ÉÔ¤²â£¬Í¨¹ý¾«È·µÄÏßÐÔ·Ö×Ó½«D4RÁý·Ö×ÓÁ¬½ÓÆðÀ´£¨e.g.,1 and 2£©£¬¿ÉÒԺϳɣ¬¾ßÓÐÓëACOÀàËÆµÄ¾Ö²¿»ú¹¹µÄ¾ÛºÏÎïÍøÂç¡£ |
3Â¥2015-03-23 12:35:03














»Ø¸´´ËÂ¥