Synthesis and Properties of Spiro[dibenzo[a, j]xanthene-14,9'-fluorene]

doi:10.7503/cjcu20130375

Abstract

Abstract:

Spiro[fluorene-9,9'-xanthene](SFX) and its derivatives as the unit of organic optoelectronic materials have attracted much attention due to their promising thermal and photophysical properties. By tuning the conjugated degree and the steric of SFX, we designed a novel compound spiro[dibenzo[a,j]xanthene-14,9'-fluorene] and anticipated that it would have better performance than SFX. The reaction of 9H-fluoren-9-one and naphthalen-2-ol under the conditions of sulfuric acid and 3-mercaptopropanoic acid gave the target compound spiro[dibenzo[a,j]xanthene-14,9'-fluorene]. The compound was characterized by NMR, MS, IR spectra, elemental analysis and X-ray structural determination. The crystal data of the compound showed that a spiro ring was formed through the six-membered heterocyclic ring in dibenzo[a,j]xanthene sharing one carbon atom with the five-membered ring in fluorene. The photophysical and thermal properties were investigated by UV-Vis absorption, photoluminescence spectra, thermogravimetric analysis(TGA) and differential scanning calorimetry(DSC). The maximum emission wavelength of the compound was found at 366 nm, and it showed a high thermal stability with a melting point of 297 ℃ and a decomposition temperature of 329 ℃. The results indicated that spiro[dibenzo[a,j]xanthene-14,9'-fluorene] could be used in the organic optoelectronic polymers to enhance their performance.

Key words: Spiro ring, Xanthene, Fluorene, Crystal structure

CLC Number:

O621.3

TrendMD:

CHEN Muzi, YOU Yongzhi, ZHANG Yong, LI Haiyan, FANG Wei. Synthesis and Properties of Spiro[dibenzo[a, j]xanthene-14,9'-fluorene][J]. Chem. J. Chinese Universities, 2014, 35(1): 63.

Figures/Tables 7

Fig.1 Molecular structure of spiro[dibenzo[a,j] xanthene-14,9'-fluorene]

Table 1 Crystallographic data and refinements for spiro[dibenzo[a,j]xanthene-14,9'-fluorene]

Empirical formula	C₃₃H₂₀O	V/nm³	4.4191(11)
Formula weight	432.49	Z	8
Temperature/K	293(2)	D_c/(g·c $m - 3$ )	1.300
λ(Mo Kα)/nm	0.071070	Absorption coefficient/mm^-1	0.077
Crystal system, space group	Orthorhombic, Pbcn	F(000)	1808
a/nm	1.6599(2)	Crystal size	0.80 mm×0.60 mm×0.10 mm
b/nm	0.78609(11)	2θ_max/(°)	3.11—25.34
c/nm	3.3867(5)	Number of reflns. collected	16281
α/(°)	90.00	Number of indep. reflns	3823
β/(°)	90.00	Goodness-of-fit on F²	1.100
γ/(°)	90.00	Final R[I>2σ(I)]	0.0987, 0.1672

Table 1 Crystallographic data and refinements for spiro[dibenzo[a,j]xanthene-14,9'-fluorene]

Empirical formula	C₃₃H₂₀O	V/nm³	4.4191(11)
Formula weight	432.49	Z	8
Temperature/K	293(2)	D_c/(g·c $m - 3$ )	1.300
λ(Mo Kα)/nm	0.071070	Absorption coefficient/mm^-1	0.077
Crystal system, space group	Orthorhombic, Pbcn	F(000)	1808
a/nm	1.6599(2)	Crystal size	0.80 mm×0.60 mm×0.10 mm
b/nm	0.78609(11)	2θ_max/(°)	3.11—25.34
c/nm	3.3867(5)	Number of reflns. collected	16281
α/(°)	90.00	Number of indep. reflns	3823
β/(°)	90.00	Goodness-of-fit on F²	1.100
γ/(°)	90.00	Final R[I>2σ(I)]	0.0987, 0.1672

Fig.2 ORTEP diagram of spiro[dibenzo[a,j] xanthene-14,9'-fluorene]

Table 2 Selected bond lengths(nm) and bond angles(°) for spiro[dibenzo[a,j]-xanthene-14,9'-fluorene]

O1—C10	1.366(6)	C20—C21	1.549(6)
O1—C11	1.390(5)	C21—C22	1.525(6)
C1—C21	1.563(5)	C21—C33	1.547(6)
C10—O1—C11	119.8(3)	C20—C21—C22	113.2(3)
C1—C21—C20	109.8(3)	C20—C21—C33	111.3(3)
C1—C21—C22	112.2(3)	C22—C21—C33	101.3(3)
C1—C21—C33	108.7(3)

Table 3 Selected dihedral angles(°) for spiro[dibenzo[a,j]xanthene-14,9'-fluorene]

C28—C29—C30—C31—C32—C33 and C22—C23—C24—C25—C26—C27	3.301(141)
C1—C2—C3—C4—C5—C6—C7—C8—C9—C10 and C22—C23—C24—C25—C26—C27	88.261(114)
C1—C2—C3—C4—C5—C6—C7—C8—C9—C10 and C28—C29—C30—C31—C32—C33	85.375(113)
C11—C12—C13—C14—C15—C16—C17—C18—C19—C20 and C22—C23—C24—C25—C26—C27	89.272(119)
C11—C12—C13—C14—C15—C16—C17—C18—C19—C20 and C28—C29—C30—C31—C32—C33	87.687(119)

Fig.3 UV-Vis absorption(a) and emission(b) spectra of spiro[dibenzo[a,j]xanthene-14,9'-fluorene] in C2H5OH(1×10-6 mol/L)

Fig.4 TGA(A) and DSC(B) curves of spiro[dibenzo[a,j]xanthene-14,9'-fluorene]

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