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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 ¡£

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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.
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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.
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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
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