Syntheses, Structure, and Photoluminescence Properties of the
1-Dimensional Chain Compounds [(TPA)<sub>2</sub>Au][Au(CN)<sub>2</sub>] and (TPA)AuCl
(TPA = 1,3,5-Triaza-7-phosphaadamantane)
Zerihun Assefa
Mohammad A. Omary
Brian G. McBurnett
Ahmed A. Mohamed
Howard H. Patterson
Richard J. Staples
John P. Fackler
10.1021/ic025784r.s001
https://acs.figshare.com/articles/journal_contribution/Syntheses_Structure_and_Photoluminescence_Properties_of_the_1-Dimensional_Chain_Compounds_TPA_sub_2_sub_Au_Au_CN_sub_2_sub_and_TPA_AuCl_TPA_1_3_5-Triaza-7-phosphaadamantane_/3609093
The structures and temperature-dependent photoluminescence properties of the one-dimensional compounds
[(TPA)<sub>2</sub>Au][Au(CN)<sub>2</sub>], <b>1</b>, and (TPA)AuCl, <b>2</b>, are reported. An extended linear chain with weak Au···Au interactions
along the <i>c</i>-axis is evident in the structure of <b>1</b>, and a helical chain with a pitch of 3.271 Å is seen for <b>2</b>. The
intrachain Au···Au separation is 3.457(1) and 3.396(2) Å in <b>1</b> and <b>2</b>, respectively. As a result of this weak Au···Au
interaction, the physical properties of these compounds are anisotropic. Scanning electron microscopy (SEM) studies
indicate that single crystals of both compounds are noninsulating. Single crystals of <b>1</b> do not luminesce visibly, but
grinding the crystals finely initiates a strong green emission under UV irradiation at room temperature. Further
interesting optical properties include the dependence of the emission profile of the powder on the exciting wavelength
and luminescence thermochromism. When excited at wavelengths < 360 nm, the powder exhibits a blue emission
at 425 nm while excitation with longer wavelengths leads to a green emission near 500 nm. While the green
emission dominates at ambient temperature, cooling to cryogenic temperatures leads to the dominance of the blue
emission. Fibers of <b>2</b> are luminescent at 78 K with an emission band centered at 580 nm. Compound <b>1</b> crystallizes
in the orthorhombic space group <i>Cccm</i> (No. 66), with <i>Z </i>= 2, <i>a</i> = 6.011(1) Å, <i>b</i> = 23.877(6) Å, <i>c</i> = 6.914(1) Å,
<i>V</i> = 992.3(3) Å<sup>3</sup>, and <i>R</i> = 0.0337. Compound <b>2</b> crystallizes in the trigonal space group <i>R</i>3̄ (No. 148), with <i>Z</i> =
18, <i>a</i> = 22.587(2) Å, <i>b</i> = 22.587(2) Å, <i>c</i> = 9.814(2) Å, <i>V</i> = 4336 Å<sup>3</sup>, and <i>R</i> = 0.0283.
2002-10-31 00:00:00
425 nm
emission profile
3.271 Å
TPA
cryogenic temperatures
compound
580 nm
helical chain
space group Cccm
4336 Å 3
ambient temperature
Scanning electron microscopy
luminescence thermochromism
500 nm
SEM
Photoluminescence Properties
2 crystallizes
emission band
Single crystals
powder exhibits
78 K
wavelength
360 nm
room temperature
UV irradiation
Compound 1 crystallizes