Supramolecular Pt(II) and Ru(II) Trigonal Prismatic Cages Constructed with a Tris(pyridyl)borane Donor.
Supramolecular Pt(II) and Ru(II) Trigonal Prismatic Cages Constructed with a Tris(pyridyl)borane Donor.
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DOI：
10.1021/acs.inorgchem.8b01830
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发表时间：
2018-09-17
影响因子：
4.6
通讯作者：
Lee J
中科院分区：
文献类型：
--
作者：
Ryu JY;Lee JM;Van Nghia N;Lee KM;Lee S;Lee MH;Stang PJ;Lee J
我们报道了一个含有Lewis酸性三角硼中心的超分子笼子的新例子。以二Ru(2)或Pd(3)为电子受体的三(吡啶基)硼供体1的自组装形成了含硼的三方柱状超分子笼5和6，其结构经核磁共振氢谱、电喷雾电离飞行时间质谱学和X射线结晶学表征。确定笼5的分子结构为内径约为400ä3的三方柱笼。研究了硼烷配体1和铂笼6的氟离子结合性能。UV/Vis吸收滴定研究表明，笼6的B中心与氟离子发生了较强的结合作用，根据1：2的结合等温线估算出在丙酮中的结合常数为1.3×1010M−2。通过~1H核磁共振滴定证实了结合的存在。光致发光滴定研究表明，笼6发出以硼烷为中心的荧光(τ=2.21 ns)，随着氟化物的加入，该荧光逐渐熄灭。然而，当过量的氟加入到6的溶液中时，观察到吡啶配体从铂(II)中心解离。C3对称的三(吡啶基)硼烷配体与二Ru或铂电子受体的自组装导致了三方柱状超分子笼子的形成。硼集中在配体和铂笼中，很容易与氟离子络合，在添加氟离子时表现出关闭的荧光响应。
We report a novel example of supramolecular cages containing a Lewis acidic trigonal boron center. Self-assembly of the tris(pyridyl)borane donor 1 with diruthenium (2) or platinum (3), as an electron acceptor, furnished boron-containing trigonal prismatic supramolecular cages 5 and 6, which were characterized by 1H NMR and electrospray ionization time-of-flight mass spectroscopy and X-ray crystallography. The molecular structure of cage 5 was confirmed as a trigonal prismatic cage with an inner dimension of about 400 Å3. The fluoride binding properties of borane ligand 1 and Pt cage 6 were studied. UV/Vis absorption titration studies demonstrated that the boron center of cage 6 undergoes strong binding interaction with the fluoride ion, with an estimated binding constant of 1.3 × 1010 M−2 in acetone based on the 1:2 binding isotherm. The binding was also confirmed by 1H NMR titration. Photoluminescence titration studies showed that cage 6 emitted borane-centered fluorescence (τ = 2.21 ns), which was gradually quenched upon addition of fluoride. When excess fluoride was added to a solution of 6, however, dissociation of the pyridyl ligand from the Pt(II) center was observed. The self-assembly of a C3-symmetric tris(pyridyl)borane ligand and diruthenium or platinum electron acceptors led to the formation of trigonal prismatic supramolecular cages. The boron centers in the ligand and the platinum cage readily complexed fluoride anions, exhibiting turn-off fluorescence responses upon the addition of fluoride anions.
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影响因子：
64.8
作者：
Fujita, Daishi;Ueda, Yoshihiro;Fujita, Makoto
通讯作者：
Fujita, Makoto
影响因子：
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作者：
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通讯作者：
Lee, Min Hyung
影响因子：
4.9
作者：
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通讯作者：
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