CN101016292A

CN101016292A - 9-(1-Benzimidazolyl)acridine CuI complex, preparing method and application thereof

Info

Publication number: CN101016292A
Application number: CN 200710056823
Authority: CN
Inventors: 卜显和; 常泽; 刘春森; 王军杰; 闫莉芬; 田金磊
Original assignee: Nankai University
Current assignee: Nankai University
Priority date: 2007-02-14
Filing date: 2007-02-14
Publication date: 2007-08-15

Abstract

The invention discloses a making method and application of 9-(1-benzimidazole) acridine complex, which is characterized by the following: the chemical formula of complex is Cu4I4L4, which is prepared by dispersing method, wherein L is 9-(1-benzimidazole) acridine; the complex possesses similar cubane structure, which possesses higher luminous strength as fluorescent material.

Description

9-(1-benzimidazolyl-) acridine CuI complex and preparation method and application thereof

Technical field

The present invention relates to transition metal complex material field, especially a kind of 9-(the 1-benzo is narrowed the azoles base) acridine ligand CuI complex and preparation method, described title complex is the title complex with class cubane structure, and its photoluminescent property makes it can be used as fluorescent material and is applied.

Background technology

Because d ¹⁰The closedshell transition metal complex has the advantages that structure is various and photoluminescent property is abundant, is widely studied in recent years.CuI becomes fabulous inorganic functional module because of forming class cubane structure and have abundant optical property in title complex, existing correlative study [M.Vitale and P.C.Ford, Coord.Chem.Rev., 2001 in the coordination chemistry field, 219-221,3.; K.R.Kyle, C.K.Ryu, J.A.DiBenedetto and P.C.Ford, J.Am.Chem.Soc., 1991,113,2954; A.Vega and J.-Y.Saillard, Inorg.Chem., 2004,43,4012.; C.K.Ryu, M.Vitale and P.C.Ford, Inorg.Chem., 1993,32,869; E.Cariati, J.Bourassa and P.C.Ford, Chem.Commun., 1998,32,1623; E.Cariati, X.Bu and P.C.Ford, Chem.Mater., 2000,12,3385.].The N atom of benzoglyoxaline has stronger coordination ability, energy and multiple metallic ion coordination, under strong coordinate bond, weak hydrogen bond and π-π effect, assemble out various metal complexess [Rom á n-Alpiste M.J., the Mart í n-Ramos J.D. of novel structure and unique properties

A.J., et al.Polyhedron, 1999,18,3341.; XieL.X., Wei Y.L., Wang Y.F., et al.Mol.Struct, 2004,602,201.; Hu R.F., Zhang J., Kang Y., et al.Inorg.Chem.Commun., 2005,8,828.; Reisner E., Arion V.B., Eichinger A., et al.Inorg.Chem., 2005,44,6704.; Murrie M., Collison D., Garner C.D., et al.Polyhedron, 1998,17,3031.].Acridine ring system row part has big conjugated pi system, often easily form good pi-pi accumulation effect when forming title complex, thereby assemble has the super molecular compound of potential application performance.[Ivana?Sloufovaa，Miroslav?Sloufb，ACTA?C，2000，C56(11)，1312.；Xian-He?Bu，Ming-Liang?Tong，Ya-Bo?Xie，et?al.Inorg.Chem.，2005，44，9837-9846.；Xian-He?Bu，Ming-Liang?Tong，Ho-Chol?Chang，et?al.Angew.Chem?Int.Ed.，2004，43，192-195.]。Introduce same part and construct the corresponding metal title complex and study the report of its photoluminescent property relative less benzimidazole and acridine ring are common.Therefore, to and the development and use of acridine-benzoglyoxaline ligand CuI complex photoluminescent property be that new road has been opened up in the exploration of novel fluorescent material.

Summary of the invention

The objective of the invention is to disclose a kind of, have 9-(1-benzimidazolyl-) acridine ligand CuI complex of class cubane structure and the application of preparation method and this title complex thereof.

Technical scheme of the present invention provides a kind of 9-(1-benzimidazolyl-) acridine CuI complex, it is characterized in that title complex is the compound of following chemical formula: Cu ₄I ₄L ₄, wherein L is 9-(1-benzimidazolyl-) acridine, its molecular formula is as follows:

The preparation method who the invention also discloses this title complex adopts diffusion process:

Under the room temperature, 9-(1-imidazolyl) acridine is dissolved in CHCl ₃In the solution, place the test tube bottom.The middle CHCl that adds ₃/ CH ₃The CN mixing solutions, the upper strata adds the CH of CuI ₃The CN saturated solution leaves standstill diffusion and obtained the orange bulk-shaped monocrystal in 30-35 days, uses CHCl ₃Washing, drying.

9-of the present invention (1-benzimidazolyl-) acridine CuI complex can be used as the application of fluorescent material aspect material.

Title complex of the present invention is easy to preparation, and the crystal purity that obtains is higher, has stable fluorescence-emission character at normal temperatures, has the absorption and the emission wavelength of feature, and has higher luminous intensity, is applied thereby can be used as fluorescent material.

Description of drawings

The crystalline structure figure of Fig. 1 title complex;

The solid fluorescence figure of Fig. 2 title complex;

The powdery diffractometry XPRD figure of Fig. 3 title complex.

Embodiment

9-of the present invention (1-benzimidazolyl-) acridine CuI complex, its crystal belongs to tetragonal system, and spacer is I4 (1)/a, and unit cell parameters is: a=23.4032 , b=23.4032 , c=13.0773 , α=β=γ=90 °; The same respectively Cu of N on each part benzoglyoxaline ring ₄I ₄A Cu coordination.

In the preparation method of 9-of the present invention (1-benzimidazolyl-) acridine CuI complex, part is dissolved in CHCl ₃In to make strength of solution be 0.01～0.02molL ^-1CHCl ₃/ CH ₃CN mixed liquor volume ratio can be: 1: 1～1: 1.5; The volume ratio of upper, middle and lower-ranking solution is 1: 6: 1～1: 8: 1.

The preparation of embodiment 1 title complex:

0.05mmol 9-(1-benzimidazolyl-) acridine is dissolved in 3ml CHCl ₃In, place the test tube bottom.The middle CHCl that adds ₃/ CH ₃CN mixing solutions (1: 1) 18ml, the upper strata adds the CH of CuI ₃CN saturated solution 3ml leaves standstill diffusion and obtained orange bulk-shaped monocrystal, crystal CHCl in 30 days ₃Washing, drying.Productive rate～50%.

The infrared analysis result: main infrared absorption peak is: 3065cm ^-1, 1607cm ^-1, 1553cm ^-1, 1508cm ^-1, 1501cm ^-1, 1456cm ^-1, 1437cm ^-1, 1419cm ^-1, 1305cm ^-1, 1288cm ^-1, 1222cm ^-1, 1194cm ^-1, 1145cm ^-1, 1004cm ^-1, 931cm ^-1, 857cm ^-1, 796cm ^-1, 746cm ^-1, 646cm ^-1

By the phase purity of XPRD detection title complex, the result is referring to Fig. 3.

The preparation of embodiment 2 title complexs:

0.04mmol 9-(1-benzimidazolyl-) acridine is dissolved in 2ml CHCl ₃In the solution, place the test tube bottom.The middle CHCl that adds ₃/ CH ₃CN mixing solutions (1: 1.25) 16ml, the upper strata adds the CH of CuI ₃CN saturated solution 2ml leaves standstill diffusion and obtained orange bulk-shaped monocrystal, crystal CHCl in 35 days ₃Washing, drying.Productive rate～45%.

The preparation of embodiment 3 title complexs:

0.04mmol 9-(1-benzimidazolyl-) acridine is dissolved in 3ml CHCl ₃In the solution, place the test tube bottom.The middle CHCl that adds ₃/ CH ₃CN mixing solutions (1: 1.5) 17ml, the upper strata adds the CH of CuI ₃CN saturated solution 3ml leaves standstill diffusion and obtained orange bulk-shaped monocrystal, crystal CHCl in 35 days ₃Washing, drying.Productive rate～43%.

The infrared analysis result: main infrared absorption peak is: 3065cm ^-1, 1607cm ^-1, 1553cm ^-1, 1508cm ^-1, 1501cm ^-1, 1456cm ^-1, 1437cm ^-1, 1419cm ^-1, 1305cm ^-1, 1288cm ^-1, 1222cm ^-1, 1194 cm ^-1, 1145cm ^-1, 1004cm ^-1, 931cm ^-1, 857cm ^-1, 796cm ^-1, 746cm ^-1, 646cm ^-1

The sign of embodiment 4 title complexs:

(1) structure determination of title complex

The monocrystalline of choosing suitable size at microscopically at room temperature carries out the X-ray diffraction experiment.On BrukerSmart 1000 CCD diffractometers, use Mo-K through the graphite monochromator monochromatization _αRay (λ=0.71073 ) is collected diffraction data in -ω mode.Carry out reduction of data with Bruker SAINT program.The diffraction data of part-structure carries out absorption correction with the SADABS program.Crystalline structure is solved in conjunction with difference Fourier is synthetic by direct method.All non-hydrogen atom coordinate and anisotropic parameters carry out the complete matrix least-squares refinement, and C-H and N-H atom site are determined by theoretical mode computation.

Complex crystal belongs to tetragonal system, and spacer is I4 (1)/a, and unit cell parameters is: a=23.4032 , b=23.4032 , c=13.0773 , α=β=γ=90 °; The same respectively Cu of N on each part benzoglyoxaline ring ₄I ₄A Cu coordination.Detailed axonometry data see Table 1.Complex structure is seen Fig. 1.

(2) photoluminescent property of title complex

The exsiccant title complex carries out fluorometric investigation after milled processed.Title complex excites at 398nm, 406nm place, all obtains emission peak at 439nm, 446nm place.See Fig. 2.

Empirical?formula C ₈₀H ₅₂Cu ₄I ₄N ₁₂ Formula?weight 1943.08 Crystal?system Tetragonal Space?group I4(1)/a Unit?cell?dimensions(， ⁰) a 23.4032(12) b 23.4032(12) c 13.0773(13) α， 90 β 90 γ 90 Volume( ³) 7162.6(9) Z 16 D _calcd(g/cm ³) 1.802 μ(mm ^-1) 2.950 F(000) 3776 Range?of?h，k，l -25/30，-30/25，-17/17 Reflections?collected/unique 23685/4274 Max.&min.transmission 0.7373?and?0.6659 Data/restraints/parameters 4274/0/226 Goodness-of-fit?on?F ² 1.022 Final?R?indices[I＞2σ(I)] R1＝0.0359，wR2＝0.0681 R?indices(all?data) R1＝0.0820，wR2＝0.0812 Largest?diff.peak&hole(e/ ³)?0.397?and?-0.484

Table 1

Claims

1, a kind of 9-(1-benzimidazolyl-) acridine CuI complex is characterized in that title complex is the compound of following chemical formula: Cu ₄I ₄L ₄, L=9-(1-benzimidazolyl-) acridine wherein, its molecular formula is as follows:

2, according to the described 9-of claim 1 (1-benzimidazolyl-) acridine CuI complex, it is characterized in that the crystal of described title complex belongs to tetragonal system, spacer is I4 (1)/a, unit cell parameters is: a=23.4032 , b=23.4032 , c=13.0773 , α=β=γ=90 °; The same respectively Cu of N on each part benzoglyoxaline ring ₄I ₄A Cu coordination.

3, the preparation method of the described 9-of claim 1 (1-benzimidazolyl-) acridine CuI complex is characterized in that it comprises the steps: under the room temperature, and part 9-(1-imidazolyl) acridine is dissolved in CHCl ₃In, place the test tube bottom; The middle CHCl that adds ₃And CH ₃The CN mixing solutions, the upper strata adds the CH of CuI ₃The CN saturated solution at room temperature leaves standstill diffusion and obtained the orange bulk-shaped monocrystal in 30-35 days, uses CHCl ₃Washing, drying.

4,, it is characterized in that part 9-(1-imidazolyl) acridine is dissolved in CHCl according to the preparation method of the described 9-of claim 3 (1-benzimidazolyl-) acridine CuI complex ₃In to make strength of solution be 0.01～0.02molL ^-1

5, according to the preparation method of the described 9-of claim 3 (1-benzimidazolyl-) acridine CuI complex, it is characterized in that CHCl ₃And CH ₃CN mixed liquor volume ratio: 1: 1～1: 1.5.

6, according to the preparation method of claim 3 or 4,5 described 9-(1-benzimidazolyl-) acridine CuI complex, the volume ratio that it is characterized in that upper, middle and lower-ranking solution is 1: 6: 1～1: 8: 1.

7, the described 9-of claim 1 (1-benzimidazolyl-) acridine CuI complex aspect material as the application of fluorescent material.