Four new luminescent organoboron complexes have been synthesized and fully characterized. These compounds are four-coordinate boron chelated by either 8-hydroxyquinolato (q) or functionalized 8-hydroxylquinolato ligands, including BPh2(5-(1-naphthyl)-q) (1), BPh2(5-(2-benzothienyl)-q) (2), B(2-benzothienyl)2q (3), and B(2-benzothienyl)2(2-Me-q) (4). All four compounds have a tetrahedral geometry as established by X-ray diffraction analyses. In solution, compounds 1-4 have an emission maximum at 534, 565, 501, and 496 nm, respectively, at room temperature. They emit similar colors in the solid states without red shifts of the emission band due to the lack of significant intermolecular interactions in the crystal lattices. The substituent group at C5 or C2 position of the 8-hydroxyquinolato ligand has been observed to have a significant impact on the emission energy and the emission quantum efficiency of the boron complexes. Molecular orbital calculations (Gaussian 98) showed that the electronic transition of 1 and 2 is a pi-pi* transition centered on the functionalized 8-hydroxyquinolato group and the electronic transition of 3 and 4 is an interligand charge transfer from the 2-benzothienyl ligand to the hydroxyquinolato ring. A double-layer electroluminescent device using 3 as the emitter has been fabricated, which produced a broad emission band with a significant contribution of exciplex emission.
Eight novel three-coordinate boron compounds with the general formula BAr(2)L, in which Ar is mesityl and L is a 7-azaindolyl- or a 2,2'-dipyridylamino-functionalized aryl or thienyl ligand, have been synthesized by Suzuki coupling, Ullmann condensation methods, or simple substitution reactions (L = p-(2,2'-dipyridylamino)phenyl, 1; p-(2,2'-dipyridylamino)biphenyl, 2; p-(7-azaindolyl)phenyl, 3; p-(7-azaindolyl)biphenyl, 4; 3,5-bis(2,2'-dipyridylamino)phenyl, 5; 3,5-bis(7-azaindolyl)phenyl, 6; p-[3,5-bis(2,2'-dipyridylamino)phenyl]phenyl, 7; 5-[p-(2,2'-dipyridylamino)phenyl]-2-thienyl, 8). The structures of 1, 3, and 5-7 have been determined by X-ray diffraction analyses. These new boron compounds are bright blue emitters. Electroluminescent devices using compound 2 or 8 as the emitter and the electron-transport layer have been successfully fabricated. Molecular orbital calculations (Gaussian 98) have established that the blue emission of compounds 1-8 originates from charge transfer between the pi orbital of the ligand L and the p(pi) orbital of the boron center. The ability of these boron compounds to bind to metal centers to form supramolecular assemblies was demonstrated by treatment of compound 2 with Zn(O(2)CCF(3))(2), which generated a 1:1 chelate complex [2.Zn(O(2)CCF(3))(2)] (10), and also by treatment of compound 4 with AgNO(3), yielding a 2:1 coordination compound [(4)(2).Ag(NO(3))] (11). In the solid state, compounds 10 and 11 form interesting head-to-head and tail-to-tail extended structures that host solvent molecules such as benzene.
A comprehensive study of a series four‐coordinate boron compounds with the general formula of BPh2(N,N), where N,N are bidentate chelate ligands containing both neutral and negatively charged nitrogen donor atoms has been conducted. The structures of the boron complexes were examined via single‐crystal X‐ray diffraction. The series of molecules display bright luminescence with emission maxima λmax ranging from blue to red, depending on the nature of the N,N chelate ligand. The electronic effects and their consequences on the luminescent properties of the complexes due to the CH replacement of the chelate ligand by a nitrogen atom, the increase of conjugation, or the change of substituents on the chelate ligand have been examined using electrochemical analysis, UV‐visible, and fluorescence spectroscopic methods, and by molecular orbital calculations (Gaussian 98). Experimental data and MO calculation results established that the emission of this class of compounds is caused by π–π* transitions centered on the chelate ligand. Furthermore, the experimental and theoretical results consistently and conclusively established that electron withdrawing groups on the negatively charged N‐donor portion of the chelate ligand causes a decrease in the highest occupied molecular orbital (HOMO) energy level, thus increasing the energy gap. The CH replacement by a nitrogen atom on the negatively charged portion of the chelate ligand causes a dramatic decrease of the HOMO energy level, and the increase of conjugation in the chelate ligand significantly decreases the energy gap. Blue and red electroluminescent (EL) devices were fabricated successfully using two representative boron compounds from the series. The new boron compounds have been found to be able to function as both emitters and electron transport materials in EL devices.
Three new 2,2'-dipyridylamino functionalized pyrene derivatives, 1-pyrenyl-2,2'-dipyridylamine (1), 4-(1pyrenyl)phenyl-2,2'-dipyridylamine (2), and 4-[4'-(1-pyrenyl)biphenyl]-2,2'-dipyridylamine (3) have been synthesized and fully characterized. For comparison of electronic properties, a diphenylamino functionalized molecule 4-[4'-(1-pyrenyl)biphenyl]diphenylamine (4) has also been synthesized. Compounds 1-4 are bright blue emitters in solution and in the solid state with l max at y420-460 nm and a high emission efficiency in solution. All four compounds form amorphous glasses with T g values of 66 uC, 79 uC, 165 uC, and 98 uC, respectively. The electronic properties of the four compounds were examined by spectroscopic methods, cyclic voltammetry and Gaussian 98 molecular orbital calculations. The utilities of this class of molecules in OLEDs have been demonstrated by EL devices of compounds 3 and 4, which showed that 3 can function as a bright blue emitter and an electron transport material in a double-layer device while 4 can function as a bright blue emitter and a hole transport molecule in a triple-layer device. The dipyridylamino functional group in molecules 1-3 are capable of chelating to metal ions such as Zn(II) as demonstrated by the synthesis and structure of the complex [2?(Zn(O 2 CCF 3 ) 2 ] 2 (5). The binding of Zn(II) ions to the dipyridyl group causes a reduction of the emission efficiency of the ligand 2.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
customersupport@researchsolutions.com
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.