Crystal Lattice Design of H2O-Tolerant n-Type Semiconducting Dianionic Naphthalenediimide Derivatives
Crystal Lattice Design of H2O-Tolerant n-Type Semiconducting Dianionic Naphthalenediimide Derivatives
复制标题
DOI：
10.1021/jacs.0c11545
复制
发表时间：
2021-01-20
影响因子：
15
通讯作者：
Akutagawa, Tomoyuki
中科院分区：
文献类型：
--
作者：
Abe, Haruka;Kawasaki, Ayumi;Akutagawa, Tomoyuki
双阴离子双（丙酸）-萘二酰亚胺（PCNDI 2-）形成简单的（M+）（2）（PCNDI 2-）中心点（H2O）（n）（M+ = Li+、Na+、K+、Rb+和Cs+）的2：1阳离子-阴离子盐，由于其静电结合晶格的存在，表现出可逆的H2O吸附-脱附行为。最大H2O吸附量（n）为M+ = Li+，Na+，K+，Rb+，和Cs+分别为0.25，6.0，4.0，6.0，和2.0，而可逆的开（关）门H2O吸附-脱附等温线在273和298 K，除了M+ = Li+。在M+ = Na+和K+盐中观察到约10（-4）-10（-5）S cm（-1）的高离子电导率，而在M+ = Rb+和Cs+的大阳离子中观察到短程热涨落。M+ = Na+和K+盐在H2O吸附-脱附循环过程中的静电晶格能的变化明显大于M+ = Rb+和Cs+。因此，Na+和K+盐具有相当灵活的静电晶格，在H2O吸附循环期间具有大幅度的晶格调制。与此相反，晶格调制M+ = Rb+和Cs+盐涉及低幅度的离子位移，形成一个相对刚性的阳离子-阴离子静电晶格。的闪光光解时间分辨微波电导率和过渡吸收光谱的结果表明，高的电子迁移率的H2O吸附的薄膜，其中结晶的H2O分子不作为电子捕获网站。电子迁移率随Cs ~+的增加而增大，其大小顺序为Rb ~+ > K ~+ > Na ~+ > Li ~+。
Dianionic bis(propionate)-naphthalenediimide (PCNDI2-) formed simple 2:1 cation-anion salts of (M+)(2)(PCNDI2-)center dot(H2O)(n) (M+ = Li+, Na+, K+, Rb+, and Cs+), which exhibited reversible H2O adsorption-desorption behavior because of the presence of their electrostatically binding crystal lattices. The maximum H2O adsorption amounts (n) for M+ = Li+, Na+, K+, Rb+, and Cs+ were 0.25, 6.0, 4.0, 6.0, and 2.0, respectively, whereas the reversible gate-opening (gate-closing) H2O adsorption-desorption isotherms were observed at 273 and 298 K, except for M+ = Li+. High ionic conductivities of around 10(-4)-10(-5) S cm(-1) were observed in M+ = Na+ and K+ salts, whereas short-range thermal fluctuations occurred in large cations of M+ = Rb+ and Cs+. The change in the electrostatic lattice energy for M+ = Na+ and K+ salts during the H2O adsorption-desorption cycles was significantly larger than those for M+ = Rb+ and Cs+. Therefore, the Na+ and K+ salts had a considerably flexible electrostatic crystal lattice with a large amplitude of lattice modulation during the H2O sorption cycle. In contrast, the lattice modulation for M+ = Rb+ and Cs+ salts involved a low magnitude of ion displacements, forming a relatively rigid cation-anion electrostatic crystal lattice. The flash-photolysis time-resolved microwave conductivity and transition absorption spectroscopy results revealed the high electron mobility of H2O-adsorbed thin films, wherein the crystallized H2O molecules did not act as electron-trapping sites. The values of electron mobility increased in the order of Cs+ approximate to Rb+ > K+ > Na+ > Li+.