Journal of Molecular Structure: THEOCHEM 722 (2005) 161168 www.elsevier.

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Theoretical studies of ground and excited electronic states of OLED material bis(2-methyl-8-quinolinolato)gallium(iii) chlorine
Hong-Ze Gaoa,*, Zhong-Min Sub
a b

Fundamental Department, Chinese Peoples Armed Police Force Academy, Langfang 065000, Hebei province, China Institute of Functional Material Chemistry, Northeast Normal University, Changchun 130024, Jilin Province, China Received 9 October 2004; accepted 1 December 2004 Available online 19 March 2005

Abstract By means of ab initio HF and DFT B3LYP methods, the structure of bis(2-methyl-8-quinolinolato)gallium(III) chlorine complex(GaMq2Cl) was optimized and the electronic transition mechanism was studied in the complex. The lowest singlet excited state (S1) of GaMq2Cl has been studied by the singles conguration interaction (CIS) method and time-dependent density functional theory (TDDFT). The lowest singlet electronic transition (S0/S1) of GaMq2Cl is pp* electronic transitions and primarily localized on the phenol and pyridyl ligands. The emission of GaMq2Cl is due to the electron transitions from the phenol donor to the pyridyl acceptor including C/C and O/N transference. Two possible electron transfer pathways are presented, one by carbon, oxygen and nitrogen atoms, and the other via metal cation Ga3C. The comparison between the CIS optimized excited-state structure and the Hartree-Fock ground-state structure indicates that the geometric shift is mainly conned to the one quinoline and these changes can be easily understood in terms of the nodal patterns of the highest occupied and lowest unoccupied molecular orbitals. TD-B3-LYP calculations predict an emission wavelength of 504.57 nm. This is comparable to GaMq2Cl 492 nm observed experimentally for photoluminescence. Lending theoretical corroboration to recent experimental observations and supposition, the nature of the electron transition mechanism was revealed. q 2005 Elsevier B.V. All rights reserved.
Keywords: Bis(2-methyl-8-quinolinolato)gallium(III) chlorine complex; Ab initio; TD-DFT; Electronic transition mechanism

1. Introduction Organic light-emitting diodes (OLEDs) are heterojunction devices in which layers of organic transport materials are usually incorporated into devices as amorphous thin solid lms. These devices normally consist of at least one hole-transport layer and one electron-transport layer forming an organic/organic heterojunction. Holes from the anode and electrons from the cathode travel through the transport layers until they form a singlet exciton that relaxes giving rise to electroluminescence. Research into organic materials for use in OLEDs has been mostly focused on conjugated polymers [1,2] or low molecular weight materials [3]. In 1987, Tang and VanSlyke, [4] reported the rst efcient low

* Corresponding author. Tel.: C86 3162068419; fax: C86 3162069584. E-mail addresses: gaohongze@wjxy.edu.cn (H.-Z. Gao), zmsu@ nenu.edu.cn (Z.-M. Su). 0166-1280/$ - see front matter q 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.theochem.2004.12.040

molecular weight OLED. Following the initial report, metaloquinolates have become the focus of new electroluminescent materials research, [5,6] with Alq3 being the most often used [7]. Generally, a heavy metal ion in the same group of the periodic table gives a metal-chelate complex with low uorescent intensity. For example, tris(8-hydroxyquinolinato)gallium (Gaq3) has a weaker uorescence than Alq3. Therefore, Gaq3 and other gallium complexes have seldom been used in OLEDs. But a gallium complex with a modied molecular structure (GaMq2Cl) which with two parts of 2-methyl-8hydroxyquinoline (Mq) and a chlorine as ligands, showed strong bluegreen uorescence. It also exhibited high performance as an emitting material, an electron transport material, and a host material [8]. The photoluminescent peak of GaMq2Cl at 492 nm was as strong in intensity as that of tris (8-hydroxyquinolinato) aluminum (Alq3). The OLED using GaMq2Cl as an emitting material showed bluegreen luminance of 10,490 cd/m2. When it was used as an electron transport material in

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a rubrene doped cell, an OLED with a high luminance of 27,700 cd/m2 was obtained. The PL peak wavelength of GaMq2Cl was 51 nm shorter than that of Gaq3 (PL peak wavelength of Gaq3: 543 nm).GaMq2Cl had a steric hindrance compared with Gaq3 because of the existence of the methyl group in 2-methyl-8-hydroxyquinoline may be the one reason. In order to reveal the nature of both the ground and the excited states involved in the absorption and/or photoemission, lend theoretical corroboration to recent experimental observations and supposition, we carried out calculations of the geometry and electronic properties of GaMq2Cl in neutral state, as well as the bonding characteristics in the complex. The main difculties against a reliable computational appoach are related to the system and to the presence of strong electron correlation effects. Both properties are difcult to treat in the framework of the quantum mechanical methods rooted in the Hartree-Fock (HF) theory. As a matter of fact, the post-Hartree-Fock methods needed to obtain reliable excited states properties have scaling properties with the number of electrons (N6 or worse) that prevent their application to large systems. Recently, investigations have been carried out at the approximate level of theory (semi-empirical models) [9,10] or obtained by a reduction of the size of the system [11]. On the other hand, density functional theory (DFT) successful at providing a means to evaluate a variety of ground-state properties with an accuracy close to that of post-HF methods [12,13]. As a consequence, there is currently a great interest in extending DFT to excited electronic states [14]. In this context, the time dependent DFT approach (TDDFT) offers a rigorous route to the calculation of vertical electronic excitation spectra [1517]. Furthermore, remarkable structural predictions have been obtained especially using the hybrid density functionals [18,19] such as B3LYP and B3PW91 combining exact exchange with gradient-corrected density functionals. For excited states of closed shell molecules, time-dependent DFT methods (TDDFT) have been developed. Applications of TDDFT approaches have recently been reported on transition metal complexes and get a considerably good result [2023]. Gaussian offers the Conguration Interaction approach, modeling excited states as combinations of single substitutions out of the Hartree-Fock ground state and the method is thus named CIS [24]. When paired with a basis set, it also may be used to dene excited state model chemistries whose results may be compared across the full range of practical systems. Theoretical investigations on excited states are uncommon but necessary for the molecules used in organic light emitting diode devices (OLEDs), because the calculation of excited-state properties typically requires signicantly

more computational effort than is needed for the ground states. More over, CIS is nearly the only approach to optimize the excited state geometries for the organic light emitting complexes and materials which have practically applied value. In the present work, the CIS method is adopted to study the rst singlet excited state (S1) of GaMq2Cl. The excitedstate equilibrium geometry is compared with the optimized ground-state structure. More accurate estimates of the excitation energies for the complex were computed using time-dependent density functional theory with a hybrid functional. Assisting in the interpretation of results of the ground state and excited state, the luminescent nature of metal Ga complex was to be understood.

2. Methods of calculation All the results presented in this work were obtained at the ab initio HF and DFT B3LYP levels of theory by means of GAUSSIAN 98 program [25] Beckes three parameters hybrid method [19] using the Lee-Yang-Parr correlation function [18] was employed for all the density functional calculations. The structure of GaMq2Cl was optimized and its frontier molecular orbital characteristics and energy levels have been analyzed systematically in order to study the electronic transition mechanism in the complex. The calculation model are shown in Fig. 1, A and B represent different quinoline ligand in the compound, respectively. The structures of the complex were fully optimized using sequence of basis sets of increasing exibility including the splitvalence 6-31G, both 6-31G* basis sets. The structures of GaMq2Cl were optimized in the rst singlet excited state (S1) using conguration interaction with all singly excited determinants [24] (CIS) in the frozen-core approximation and the 6-31G* basis set. On the basis of the CIS-optimized structure of the excited state, TD-B3-LYP calculations predict an emission wavelength. And an absorption wavelength was predicted on the optimization geometry of B3LYP/6-31G*.

H3C O Cl N Ga N O
A

8 9

6 1 2

5 4 3

CH3

Fig. 1. The schematic structure.

H.-Z. Gao, Z.-M. Su / Journal of Molecular Structure: THEOCHEM 722 (2005) 161168 Table 1 Geometrical parameters optimized for GaMq2Cl Bond distance ) (A GaNA GaNB GaOA GaOB HF/6-31G* GaMq2Cl B3LYP/ 6-31G 2.1002 2.1002 1.9040 1.9039 B3LYP/ 6-31G* 2.1016 2.1016 1.9042 1.9042 Gaq3[26] B3LYP/ 6-31G 2.1080 1.9330

163

the interaction between gallium and nitrogen atoms become weaker in some extent. 3.1.2. Molecular orbitals 3.1.2.1. Orbital population. For metal chelate, the structure of the ground state and excited state, electron transition and the energy transfer mechanism and so on have pronounced effect on its EL efciency. In order to explore the electron transition property of GaMq2Cl, we made a systematic analysis on the population of GaMq2Cl molecular orbitals. It was based on the stable geometrical structure optimized at the ab initio HF/6-31G* and B3LYP/6-31G* levels. Meanwhile, the square sum of all kinds of atoms or molecular parts in GaMq2Cl indicates the contribution of each atom or molecular moiety to one molecular orbital. All the atoms in GaMq2Cl were divided into seven parts: (1) gallium atom; (2) phenol ring, including oxygen atom and atoms with numbers from 1 to 6 and mating hydrogen atoms; (3) pyridine ring, including nitrogen atom and atoms with numbers from 5 to 9 and mating hydrogen atoms; (4) oxygen atom; (5) nitrogen atom; (6) chlorine atom; (7) methyl. 10 orbitals extracted from the frontier occupied orbitals and unoccupied orbitals, respectively. The results are summarized in Tables 2 and 3. The result analysis demonstrates that the orbital populations coincide with the two methods, which implies that the molecular theoretical results are reliable. The electron clouds of the highest occupied molecular orbital(HOMO) is concentrated on the carbon and oxygen of phenol ring in 8-hydroxyquinoline ring A and ring B. The electronic cloud is mainly composed of the p-orbital ingredient and includes oxygen about 13% or so, and few s orbital characters are

2.1169 2.1168 1.8620 1.8620

3. Results and discussion 3.1. The geometry of stationary points and electronic structure 3.1.1. Ground state structure The geometry of GaMq2Cl was optimized by means of ab inition HF and DFT B3LYP methods. The main optimized parameters of each stationary point are listed in Table 1, the serial numbers of atoms are shown in Fig. 1. The calculated results from different methods are consistency, that is to say, the results calculated are reliable. In the compound GaMq2Cl, the geometries from different methods are a little different. The bond distance Ga-OA are (B3LYP/6-31G). while in the Gaq3, the value are 1.9042 A 1.9330A(B3LYP/6-31G) [26]. It is clear that the distance between the gallium and oxygen in GaMq2Cl becomes shorter than that in Gaq3 owing to the introduction methyl to the 8-hydroxyquinoline at position 2. There is the same rule in the quinoline B as quinoline A. This shows the galliumoxygen becomes stronger, which maybe make
Table 2 The molecular orbital components of GaMq2Cl% (B3LYP/6-31G*) No. Orbital 117 116 115 114 113 112 111 110 109 108(LUMO) 107 (HOMO) 106 105 104 103 102 101 100 99 98 Orbital energy (eV) 2.4632 2.2907 2.2395 1.1018 0.7935 0.7361 K0.5159 K0.5399 K1.7054 K1.7837 K5.4581 K5.5952 K6.8875 K6.8908 K7.4505 K7.5071 K7.8544 K7.9744 K7.9912 K8.1861 Ga 0.6 4.9 39.4 60.7 2.8 1.0 0.2 0.8 0.5 1.9 0.5 2.4 0.1 0.1 1.2 1.7 10.0 3.3 2.8 3.9 Phenol ring A 9.8 18.8 12.9 7.4 40.9 42.8 30.4 30.1 12.5 12.6 42.8 42.5 32.8 34.0 1.9 8.8 21.2 32.9 21.5 26.7 Phenol ring B 9.8 18.8 12.9 7.4 40.9 42.7 30.5 30.0 12.5 12.6 42.8 42.4 33.7 33.1 1.9 8.9 21.2 32.9 21.5 26.7 Pyridine ring A 36.1 23.3 15.7 7.8 14.8 14.9 35.1 34.8 37.2 36.1 9.9 9.5 29.9 30.5 5.4 1.7 24.2 14.1 28.6 20.7

Pyridine ring B 36.1 23.3 15.7 7.8 14.9 14.9 35.3 34.7 37.2 36.0 9.9 9.4 30.8 29.7 5.4 1.7 24.2 14.2 28.5 20.7

OA 0.0 1.3 0.9 4.2 2.6 2.5 0.0 0.0 1.2 0.7 13.3 11.3 0.1 0.1 0.6 6.2 12.8 20.1 12.2 15.4

OB 0.0 1.3 0.9 4.2 2.6 2.5 0.0 0.0 1.2 0.7 13.3 11.2 0.1 0.1 0.6 6.2 12.8 20.1 12.2 15.4

NA 0.1 1.6 0.8 3.7 2.9 2.4 0.0 0.1 10.5 9.5 2.3 1.9 0.1 0.2 3.3 0.3 15.9 2.1 6.6 3.6

NB 0.1 1.6 0.8 3.7 2.9 2.4 0.1 0.1 10.5 9.5 2.3 1.9 0.1 0.2 3.3 0.3 15.9 2.1 6.6 3.6

Cl 0.1 0.4 3.1 9.8 0.1 0.2 0.0 0.1 0.4 1.4 0.8 1.9 0.7 0.0 84.5 77.6 3.5 9.8 3.1 10.9

CH3(A) 5.2 7.0 1.6 0.7 1.3 0.6 1.1 1.3 2.6 2.3 0.5 0.3 2.3 2.4 0.6 0.9 2.1 0.9 0.1 0.5

CH3(B) 5.2 7.0 1.6 0.7 1.3 0.6 1.1 1.3 2.6 2.3 0.5 0.3 2.4 2.4 0.6 0.9 2.1 0.9 0.1 0.5

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Table 3 The molecular orbital components of GaMq2Cl% (HF/6-31G*) No. Orbital 117 116 115 114 113 112 111 110 109 108 (LUMO) 107(HOMO) 106 105 104 103 102 101 100 99 98 Orbital energy (eV) 6.4527 6.3629 6.2364 5.4448 5.0872 5.0026 3.3013 3.2646 2.0313 1.9375 K7.6633 K7.7975 K8.9542 K8.9556 K10.9361 K11.0294 K11.1916 K11.2947 K11.7304 K12.1834 Gs 28.5 0.7 79.9 94.5 22.4 1.2 0.4 1.2 0.6 2.3 0.3 1.2 0.0 0.1 0.4 0.6 0.9 0.9 9.3 5.3 Phenol ring A 10.1 10.5 2.6 0.6 31.9 41.5 31.9 31.1 12.5 12.5 42.4 42.4 46.0 24.7 7.3 15.6 3.2 7.1 9.3 31.2 Phenol ring B 10.1 10.6 2.6 0.6 31.7 41.9 31.4 31.5 12.3 12.7 42.3 42.4 24.7 45.9 7.2 15.6 3.2 7.1 9.3 31.2 Pyridine ring A 24.1 35.1 3.0 1.1 11.7 15.0 35.5 34.4 36.5 34.6 10.5 10.1 42.4 22.7 18.8 37.8 0.8 15.6 25.1 12.6 Pyridine ring B 24.0 35.3 3.0 1.1 11.6 15.1 35.0 34.9 36.1 35.1 10.5 10.1 22.8 42.2 18.8 37.8 0.8 15.6 25.1 12.5 OA 0.1 0.0 0.3 0.4 1.5 1.9 0.0 0.1 0.8 0.5 9.1 7.6 0.1 0.1 3.1 7.4 2.1 3.0 2.1 17.7 OB 0.1 0.0 0.3 0.4 1.5 1.9 0.0 0.1 0.8 0.5 9.1 7.6 0.1 0.1 3.1 7.4 2.1 3.0 2.1 17.6 NA 0.3 0.4 0.6 0.4 2.0 2.1 0.1 0.1 9.2 8.3 3.2 2.8 0.2 0.2 5.8 8.8 0.1 3.9 15.6 5.9 NB 0.3 0.4 0.6 0.4 2.0 2.1 0.1 0.1 9.0 8.4 3.2 2.8 0.1 0.3 5.8 8.8 0.1 3.9 15.6 5.8 Cl 3.0 0.1 8.5 1.3 0.7 0.2 0.1 0.0 0.3 1.4 0.5 1.1 0.0 0.0 50.7 0.0 91.1 55.2 28.7 12.8 CH3(A) 2.0 6.2 0.9 0.5 1.5 1.0 1.2 1.5 3.3 2.7 0.3 0.2 1.9 1.1 0.4 0.1 0.2 0.8 1.2 1.3 CH3(B) 2.0 6.2 1.0 0.5 1.5 1.1 1.2 1.5 3.2 2.8 0.3 0.2 1.0 1.9 0.4 0.1 0.2 0.8 1.2 1.3

observed, nitrogen about 2%(B3LYP/6-31G*). While in the lower occupied orbitals, the contribution of pyridine ring is primary. the electronic clouds of the lowest unoccupied molecular orbital (LUMO) is concentrated on the pyridine ring in 8-hydroxyquinoline ring A and ring B, which is mostly composed of the p-P* orbitals of carbon and nitrogen, s orbital is very little either, including nitrogen about 10%. In the part higher unoccupied orbitals are from phenol ring. In the lower occupied orbitals, as for orbital 101, 99 et al., the contribution of nitrogen became bigger for one molecular orbital, but the gallium ingredient is still very little in addition to orbital 101, occupying about 2%, which only contributes little in deeper orbital. This shows the galliumnitrogen is weaker. We note that the two lowest unoccupied orbitals are essentiallyp* orbitals of the pyridine moieties. Whereas the substitute(-CH3) is located at the pyridine ring, so methyl has a direct effect on LUMO. Compared with the HOMO-LUMO bandgap of Gaq3(K3.3503 eV /B3LYP/631G[26]), we observed that the electron-releasing-CH3 group resulting in the increased HOMO-LUMO bandgap ( K 3.6806 eV/B3LYP/6-31G), which then leads to a decrease inlmax values. 3.1.2.2. Orbital shapes. The interpretation of observed spectral features is greatly assisted by molecular orbital calculations, which, in addition to providing orbital energies for comparison with experiment, furnish a detailed description of orbitals, including spatial characteristics, nodal patterns, and individual atom contributions. The frontier orbital levels of GaMq2Cl consist of sets of closely spaced twosome. The highest occupied molecular orbitals (HOMOs) and the lowest unoccupied molecular orbitals (LUMOs) of GaMq2Cl largely preserve the electronic

structure of the 8-hydroxyquinoline ligands with little contribution from the central gallium. For intuition, the contour plot of the orbitals for molecule are depicted in Fig. 2, including least bound HOMO orbital, second highest energy orbital (HOMOK1), lowest energy LUMO and second lowest energy orbital (LUMOC1) computed using HF/6-31G* and B3LYP/6-31G*.In the contour plots, the HOMO localized over the phenoxide both in A and B, the LUMO are seen to be mainly localized over the pyridine both in A and B. Thus there must be a mixture intra 8-hydroxyquinoline and inter 8-hydroxyquinoline rings when transition from ground state to excited state. The ionization energy of the GaMq2Cl has been reported to be 5.86 eV[8], within Koopmans approximation[27],this value can be compared to the computed the least bound HOMO orbital energy from B3LYP/6-31G*, agreeing within ca. 0.4 eV. 3.2. S0/S1 Excitation energy and the s1 excited-state structure Experimental investigations of the excited-state properties of GaMq2Cl have been made on the photoluminescence, and electroluminescence of this OLED material[8]. Inspection of the emission spectras from GaMq2Cl in condensedphase systems shows that both the EL and PL spectrum have a similar shape, a photoluminescent peak at 492 nm. The results presented here support the localized nature of the orbitals involved in the lowest energy electronic transitions in GaMq2Cl. The lowest electronic transitions are p/p* transitions in the different quinolate rings and intra quinolate ring, involving partial charge transfer from the phenoxide side to the pyridyl side. There are two ways of

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165

Fig. 2. Molecular orbital surfaces of the HOMO, second highest energy molecular orbital (HOMOK1), LUMO and second lowest energy molecular orbital (LUMOC1) of GaMq2Cl.

electron transfer: one is the direct transition through carbon in quinoline ring; the other is through the metal ion, which is not only a support but also a bridge of electron transfer. 3.2.1. S0/S1 Vertical excitation energy In the present study, conguration interaction with all single (CIS) excited determinants is employed to study the lowest energy singlet excited state (S1) of GaMq2Cl. CIS represents for excited states a general zeroth-order method, just as Hartree-Fock is for the ground state of molecular systems. Besides being relatively inexpensive, permitting it to be applied to large molecules such as Alq3, analytic derivatives are available for CIS allowing the efcient calculation of excited-state structures and properties [24]. The vertical excitation energies of GaMq2Cl computed using CIS are presented. The CIS/6-31G* vertical excitation energies of GaMq2Cl varies from 3.7 to 5 eV. CIS theory is known to overestimate electronic excitation energies, due to the neglect of the effects of electron correlation and higher order excitations. To investigate the effect of electron correlation on the computed energies, calculations using time-dependent density functional theory and the hybrid density functional, B3-LYP, were carried out with the 6-31G* basis set for GaMq2Cl, so direct comparison with the CIS/6-31G* results can be made. Pople and co-workers [24] observed that with the CIS method, the use of basis sets that included signicant polarization resulted in a larger overestimation of excitation energies; however, the excitedstate potential energy surface was found to be more accurate. This behavior was attributed to the fact that these functions lower the ground-state reference energies to a greater extent than the excited-state energies do. With the prerequisite ground-state DFT calculation in hand, we proceed to the time-dependent calculation of GaMq2Cl to nd the characters and energies of its low-lying singlet and triplet excited states. We begin with the singlet/singlet spin-allowed transition. Ten singlet excited

states are calculated at the optimized structure of the ground state(B3LYP/6-31G*) for the complex and only the singlet excited states with the greatest oscillator strengths are listed as analysis example in Table 4. The energy of each excited is vertical excitation energy in electron-volts (eV) from the ground state. There are signicant oscillator strength throughout the 3w5 eV region, No excited states or absorption features are found below 2 eV. The 10 lowest-energy triplet excited states were also calculated, using analogous TD-DFT methodology. The rst ve triplet excited states are listed in Table 4. LLCT excited states are all seen, but most of them are the mixed character excited states, as with the singlets. As expected from Hunds rule, transitions to the triplet states tend to be lower in energy than their corresponding singlets. For example, the rst triplet vertical transition energy is 2.28 eV lower than that of the rst singlet excited state (3.09 eV) where both represent (predominantly) a MO 107/MO 108 transition. A commonly used model of an excited state corresponds to excitation of an electron from an occupied to a virtual MO (i.e., a one-electron picture). However, the excited states calculated herein demonstrate that excited-state electronic structures are best described in terms of multicongurations, wherein a linear combination of several occupied-to-virtual MO excitations comprises a given optical transition. Assignment of the character of each excited state was based on the compositions of the occupied and virtual MOs of the dominant conguration(s) for that excited state. For example, for S1 excited state the dominant excitation is 107/108 and since the occupied orbital (107) is phenoxide-based and the virtual orbital (108) is pyridyl p*, the transition is designated a phenoxide-to-pyridyl ligand charge transfer (LLCT). 3.2.2. S1 Excited-state structure Studies of the excited-state properties for a number of molecules using the CIS method have found that despite

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Table 4 Selected Calculated Excitation Energies (E), Wavelengths (l), Oscillator Strenghs () and Dominant excitation character for low-lying singlet (Sn) and Triplet (Tn) States of GaMq2Cl State Singlet excited states 1 2 3 4 5 Excitation 107O108 (0.65010) 3.0953 400.56 0.0868 106O108 (0.33649) 3.1771 390.24 0.0033 107O109 (0.57018) 106O108 (0.59581) 107O109(K0.37635) 106O109 (0.66328) 107O108(K0.21343) 104O109 (0.27090) 105O108 (0.32347) 106O111 (0.28291) 107O110 (0.47820) 104O108 (0.32148) 105O109 (0.27630) 106O110 (0.31232) 107O111 (0.45657) 106O110 (0.53332) 107O111 (K0.45270) 105O108 (0.10123) 106O111 (0.54277) 107O110 (K0.43399) 104O109 (K0.49002) 105O108 (0.50309) 104O108 0.0005 105O109 (K0.49675) 106O109 (0.47156) 107O108 (0.58786) 106O108 (0.51302) 107O109 (0.55198) 106O108 (0.51811) 107O109 (K0.48057) 106O109 (0.55139) 107O108 (K0.43787) 104O109 (K0.25301) 105O108 (K0.27272) 106O111 (0.40929) 107O110 (0.48184) E (eV) 3.0953 l (nm) 400.56 0.0868 Character LLCT

3.2840 3.3342 4.1803

377.54 371.85 296.59

0.0006 0.0061 0.0022

LLCT LLCT LLCT

4.1873

296.09

0.0005

LLCT

7 8

4.5284 4.5329

273.79 273.52

0.0005 0.0040

LLCT LLCT

9 10 Triplet excited states 1 2 3 4 5

4.7160 4.7171

262.90 262.84

0.0046 (0.49808)

LLCT LLCT

2.2774 2.2879 3.2693 3.2831 3.5638

544.40 541.90 379.24 377.64 347.90

0.0000 0.0000 0.0000 0.0000 0.0000

LLCT LLCT LLCT LLCT LLCT

the tendency of CIS to overestimate electronic transition energies, the excited state potential energy surface can often be quite accurate, as evidenced by comparison of equilibrium excited-state structures with experiment [24]. To investigate the geometry change associated with electronic excitation to the lowest energy singlet excited state (S0/S1), the geometry of GaMq2Cl was optimized at the CIS/6-31G* level of theory in the S1 state for comparison with the HF/6-31G* ground-state structure. Table 5 presents the optimized ground-and excited-state bond lengths for GaMq2Cl. Note that positive and negative values in the% difference columns indicate bond elongation and contraction in the excited state, respectively. Comparison of the excited-and ground-state geometries for A-, and B-quinolates in GaMq2Cl indicates that the structural shift is predominantly localized on the

B-quinolate. The A-quinolates in GaMq2Cl is practically unaffected except for changes in the AlO and AlN bond lengths. 3.2.3. Orbital analysis The lowest energy singlet transition for GaMq2Cl at the CIS/6-31G* level of theory involves transitions from the least bound HOMO orbital to the lowest and the second lowest energy LUMO orbitals with about equal weight. The least bound HOMO orbital of GaMq2Cl is mainly localized on the phenoxide, but the LUMOs also have contributions from the pyridyl, and the localized nature of the electronic excitation is clear. The observed geometry relaxation in GaMq2Cl can be rationalized by consideration of the nodal patterns of the HOMO and LUMO orbitals in Fig. 2. The lowest energy singlet excitation (S0/S1) is mainly HOMO/LUMO in character. The LUMO has nodes

H.-Z. Gao, Z.-M. Su / Journal of Molecular Structure: THEOCHEM 722 (2005) 161168 Table 5 HF/6-31G* Ground-state and CIS/6-31G* Excited-state bond lengths for the A-and B-Quinolate ligands in GaMq2Cl ) Bond distance (A HF/6-31G* A GaO GaN OC1 C1C2 C2C3 C3C4 C4C5 C5C6 NC6 C7N C7C8 C8C9 C1C6 C5C9 C7C (CH3) GaCl 1.8620 2.1169 1.3138 1.3664 1.4144 1.3610 1.4178 1.3936 1.3592 1.3057 1.4179 1.3584 1.4254 1.4157 1.5039 2.2100 B 1.8620 2.1168 1.3138 1.3664 1.4143 1.3609 1.4178 1.3936 1.3592 1.3057 1.4179 1.3584 1.4254 1.4157 1.5040 CIS/6-31G* A 1.8575 2.1474 1.3117 1.3669 1.4137 1.3610 1.4176 1.3946 1.3598 1.3066 1.4176 1.3583 1.4249 1.4147 1.5046 2.2087 B 1.9352 2.0264 1.2684 1.4351 1.3587 1.4217 1.4028 1.4105 1.3375 1.3840 1.3642 1.4124 1.4293 1.4000 1.4978 (RCIS-RHF)ORHF!100% A K0.24 1.44 K0.16 0.00 0.00 0.00 0.00 0.07 0.00 0.01 0.00 0.00 K0.01 K0.01 0.00 K0.01 B 3.93 K4.27 K3.46 5.03 K3.93 4.45 K1.06 1.21 K1.60 6.00 K3.79 3.98 0.27 K1.11 K0.41

167

across the C1C2, C3C4 bonds in the phenol ring and there has been bonding in the pyridyl ring, but the HOMO is bonding in corresponding regions and has no bonding in the pyridyl ring. Therefore one would expect elongation of these bonds and contraction in some region of pyridyl ring; Table 5 shows that these bonds are in fact considerably longer and shorter in the excited state, respectively. 3.2.4. S0/S1 Emission energy The CIS calculations for AlMq2OH also provide an estimate of the relaxed emission energy from the optimized CIS excited state structure to the Hartree-Fock ground state (S1/S0). TD-B3-LYP/6-31G* calculations were carried out for GaMq2Cl at the CIS/6-31G*-optimized excited-state structure to obtain more accurate estimates of the emission energy. We list the lowest four singlet excited states, which consists of the transition from HOMO to LUMO, and thus assigned as the localized character. With TD-B3-LYP, the emission energy is predicted to be ca. 2.4572 eV corresponding to emission at ca. 504.57 nm, which is in much closer agreement with the energy of the experimental photoluminescence emission observed in condensed-phase at ca. 492 nm [8].
State Singlet excited states 1 2 3 4 Experiment8:492 nm State Singlet Excited states 1 2 3 4 Experiment8:492 nm Excitation 107O108 106O108 107O109 106O109 Excitation 107O108 106O108 107O109 106O109 E (eV) 2.4572 2.9864 3.0741 3.3903 E (eV) 2.4572 2.9864 3.0741 3.3903 l (nm) 504.57 415.16 403.32 365.70 l (nm) 504.57 415.16 403.32 365.70

4. Conclusions The rst singlet excited state (S1) of GaMq2Cl has been studied using the CIS/6-31G* and TD-B3-LYP/6-31G* levels of theory. The electronic excitation and the structural relaxation in the excited state for GaMq2Cl has been interpreted in terms of the nature and nodal characteristics of the HOMO and LUMO. The correlation between the electronic excitation and the structural relaxation in the excited state for GaMq2Cl has been made. The S0/S1 excitation is found to be mainly localized on the quinoline ligand. At the TD-B3-LYP level of theory, the calculated wavelength for emission agree very well with the experiment. the nature of the electron transition in the complex can be interpreted from theoretical results.

Acknowledgements Thank the professor Y.S. Ji, Fundamental Department, Chinese Peoples Armed Police Force Academy, for emendating English composition.

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