Y. Yuan et al. / Polyhedron 119 (2016) 184–193
185
cells. A large number of bioactive silver complexes have been
reported [20]. It was observed that complexes having weak Ag–N
bonds usually exhibit higher bioactivity than complexes possess-
ing strong Ag–P bonds [20]. Antimicrobial activities of complexes
with Ag–X (X = P, N) can be tuned by varying the space configura-
tion of silver complexes and the number of silver atom [21]. Fol-
lowing this systematic studies on [Ag(PP)(NN)]+ complexes, we
are naturally interested in extending our investigation to analo-
gous heteroleptic silver(I) complexes and expected to obtain the
silver(I) complexes possessing bioMOFs. Here, five new polynu-
clear silver(I) complexes (containing Ag–N and Ag–P bonds) with
1,10-phenanthroline derivative and 1,3-bis(diphenylphosphino)
propane (dppp) are synthesized and the antimicrobial properties
of these complexes are detected.
Compared with the traditional spectrum technology, terahertz
spectrum has a high noise ratio and special properties such as
coherence, transient. The application of terahertz time-domain
spectroscopy (THz-TDS) gradually developed from the narrow field
(information technology, physics, materials) to a wider range of
areas (such as chemistry, biology, and medicine areas) [22–25].
Due to its sensitivity, THz spectrum can be used to detect the inter-
molecular weak interaction such as hydrogen bond, van der Waals
force, dipole rotation and vibration transition, the lattice of low-
frequency vibration and so on. THz spectroscopy has been utilized
to study the structures, configurations and environmental state of
compounds by our group [26,27].
residues were removed by filtration, and the brown filtrate was
evaporated slowly at room temperature for about one week to
yield white crystals. After phen (0.2 mmol, 0.0361 g) was added
into the stirring solution of crystals in mixing of CH2Cl2 (5 ml)
and CH3OH (5 ml) for 5 h. The insoluble residues were removed
by filtration, and the brown filtrate was evaporated slowly at room
temperature for about one week to yield white crystals. Yields:
66%. Anal. Calc. for C78H72Ag2B2F8N4O2P4: elemental analysis: C,
58.17; H, 4.47; N, 3.48%. Measured value: C, 58.85; H, 4.52; N,
3.47%. IR (cmÀ1, KBr pellets): 3550w, 3051w, 2908w, 1621m,
1587m, 1570m, 1510s, 1483s, 1434s, 1422s, 1375m, 1309m,
1275s, 1221s, 1142s, 1057vs, 955s, 844s, 820m, 757s, 745s,
730s, 697s, 645m, 547s, 511s, 480s, 444s. 1H NMR (600 MHz,
CDCl3, 298 K): d = 1.2–1.5 (m, 12H, dppp-CH2CH2CH2), 7.2–7.4
(m, with solvent signal peak overlap, dppp-ph), 7.2–7.4
(m, H3,8-phen), 7.7 (d, 4H, H5,6-phen), 8.2–8.8 (m, 4H, H2,9-phen)
ppm. 31P NMR (243 MHz, CDCl3): d = 4.8 (d, JAg–P = 420 Hz), À5.9
(d, JAg–P = 233 Hz).
2.2.2. Synthesis of {[Ag2(dppp)2(dmp)2](CF3SO3)2}n (2)
Dppp (0.2 mmol, 0.0825 g) and dmp (0.2 mmol, 0.0417 g) were
added into the stirring solution of AgCF3SO3 (0.2 mmol, 0.0514 g)
in a mixture of CH2Cl2 (5 ml) and CH3OH (5 ml) for 5 h at ambient
temperature. The insoluble residues were removed by filtration,
and the brown filtrate was evaporated slowly at room temperature
for about a week to yield white crystals. Yields: 70%. Anal. Calc. for
In this paper, we report the synthesis and characterization of di-
and poly-nuclear silver(I) complexes containing dppp, where the
versatility of coordination of silver(I) allows for a variety of coordi-
nation modes with the dppp ligand. Complexes 1–4 are of topolog-
ically promising architectures. The fluorescence spectra and THz-
TDS of complexes 1–5 have been researched in this article. In addi-
tion, complexes 1–4 show significant antibacterial activity against
the selected strains of Gram-negative (Escherichia coli) and Gram-
positive (Bacillus subtilis, Staphylococcus aureus) bacteria.
C84H76Ag2F6N4O6P4S2: elemental analysis: C, 57.48; H, 4.33; N,
3.19%. Measured value: C, 57.58; H, 4.42; N, 3.20%. IR(cmÀ1, KBr
pellets): 3434s, 3052s, 2919w, 1967w, 1620s, 1593s, 1556s,
1501vs, 1484vs, 1435vs, 1375s, 1359w, 1271vs, 1222vs, 1145vs,
1099vs, 1030vs, 998s, 956m, 854s, 804m, 783m, 743s, 729s,
698s, 636s, 571m, 548m, 513s, 478m, 445m. 1H NMR (600 MHz,
CDCl3, 298 K): d = 1.3–1.5 (m, 4H, dppp-CH2CH2CH2), 2.3–2.4 (br,
8H, dppp-CH2CH2CH2, 12H, dmp-CH3), 7.2–7.4 (m, with solvent
signal peak overlap, dppp-ph, H3,8-dmp), 7.6 (br, 4H, H5,6-dmp),
7.9–8.1 (m, 4H, H4,7-dmp) ppm. 31P NMR (243 MHz, CDCl3):
d = 1.7 (d, JAg–P = 366 Hz), À5.9 (d, JAg–P = 235 Hz).
2. Experimental section
2.2.3. Synthesis of {[Ag2(dppp)2(dmp)2](BF4)}n (3)
2.1. Materials and measurements
Follow a similar procedure as 2, dppp (0.2 mmol, 0.0825 g) and
dmp (0.2 mmol, 0.0417 g) were added into the stirring solution of
AgBF4 (0.2 mmol, 0.0384 g) in a mixture of CH2Cl2 (5 ml) and CH3-
OH (5 ml) for 5 h at ambient temperature. The insoluble residues
were removed by filtration, and the brown filtrate was evaporated
slowly at room temperature for about one week to yield white
crystals. Yields: 70%. Anal. Calc. for C83H80Ag2B2F8N4OP4: elemental
analysis: C, 59.94; H, 4.82; N, 3.37%. Measured value: C, 60.09; H,
4.87; N, 3.40%. IR (cmÀ1, KBr pellets): 3434s, 3051s, 2918s,
1620s, 1591s, 1556s, 1501vs, 1484vs, 1435vs, 1375s, 1306m,
1281m, 1221m, 1156m, 1059vs, 955s, 854s, 807s, 743s, 728m,
697vs, 647s, 548m, 513s, 480s, 444s. 1H NMR (600 MHz, DMSO,
298 K): d = 2.3–2.5 (m, 8H, dppp-CH2CH2CH2, 12H, dmp-CH3), 3.3
(br, 4H, dppp-CH2CH2CH2), 7.2–7.4 (m, with solvent signal peak
overlap, dppp-ph, H3,8-dmp), 7.7 (br, 4H, H5,6-dmp), 8.0
(br, 4H, H4,7-dmp) ppm. 31P NMR (243 MHz, DMSO): d = À4.017
(d, JAg–P = 287 Hz), À4.52 (d, JAg–P = 248 Hz).
All chemical reagents silver perchlorate (AgClO4), silver tetraflu-
oroborate (AgBF4), silver trifluoromethanesulfonate (AgCF3SO3),
1,10-phenanthroline (phen), 4,7-diphenyl-1,10-diazaphenan-
threne (Bphen), Neocuproine (dmp), 1,3-bis(diphenylphosphino)
propane (dppp) are commercially available and used without fur-
ther purification. Elemental analyses (C, H, N) were determined
on a Elementar Vario MICRO CUBE (Germany) elemental analyzer.
Infrared spectra were recorded on a Bruker EQUINOX 55 FT-IR
spectrometer using the KBr pellet in the range of 400–4000 cmÀ1
.
Excitation and emission spectra of the solid samples were recorded
on an F-4500 fluorescence spectrophotometer at room tempera-
ture. 1H and 31P NMR was recorded at room temperature with a
Varian VNMRS 600 MHz and 243 MHz spectrometer, respectively.
The THz absorption spectra were recorded on the THz time domain
device of Capital Normal University of China, based on photocon-
ductive switches for generation and electro-optical crystal detec-
tion of the far-infrared light, effective frequency in the range of
0.2–4.0 THz [28,29].
2.2.4. Synthesis of {[Ag2(dppp)2(Bphen)2](CF3SO3)2}n (4)
Follow a similar procedure as 2, dppp (0.2 mmol, 0.0825 g) and
Bphen (0.2 mmol, 0.0665 g) were added into the stirring solution of
AgOTf (0.2 mmol, 0.0514 g) in a mixture of CH2Cl2 (5 ml) and
CH3OH (5 ml) for 5 h at ambient temperature. The insoluble resi-
dues were removed by filtration, and the brown filtrate was evap-
orated slowly at room temperature for about one week to yield
white crystals. Yields: 66%. Anal. Calc. for C104H84Ag2F6N4O6P4S2:
elemental analysis: C, 62.34; H, 4.20; N, 2.80%. Measured value:
2.2. Preparation of the complexes
2.2.1. Synthesis of {[Ag2(dppp)2(phen)2](BF4)2(H2O)2}n (1)
Dppp (0.2 mmol, 0.0825 g) was added into the stirring solution
of AgBF4 (0.2 mmol, 0.0384 g) in a mixture of CH2Cl2 (5 ml) and
CH3OH (5 ml) for 5 h at ambient temperature. The insoluble