Inorganic Chemistry
Article
fluorescence microscope. Optical microscopy images were acquired on
a Leica ICC50 W microscope. Dynamic light scattering (DLS)
measurements were carried out on a Horiba SZ-100 nanoparticle
analyzer instrument operating at 22 °C.
mL), and n-hexane (10 mL) was added to precipitate a pale-yellow
solid (82 mg, 85%). 31P NMR (161.9 MHz, CDCl , ppm): −23.0. H
1
3
NMR (400 MHz, CDCl , ppm): 8.75 (dd, J = 4.0 Hz, J = 0.6 Hz, 1H,
3
H ), 8.66 (dd, J = 8.0 Hz, J = 0.8 Hz, 1H, H ), 8.37 (dt, J = 12.0 Hz, J
9
6
Small-Angle X-ray Scattering (SAXS). SAXS was performed on
the NCD beamline at the ALBA Synchrotron at 12.4 keV, and the
distance sample/detector was 2.2 m to cover the range of momentum
= 0.8 Hz, 1H, H ), 8.32 (dd, J = 11.8 Hz, J = 0.4 Hz, 1H, H ), 7.82
1
2
3
(m, 2H, H + H ), 7.28 (ddd, J = 12.0 Hz, J = 7.2 Hz, J = 0.6 Hz, 1H,
4
11
H ), 5.78 (d, J = 20.0 Hz, 1H, H , NCH N), 5.66 (dd, J = 20.0 Hz, J
10
19a
2
−1
transfer of 0.09 < q (nm ) < 5.6. The data were collected on an
= 12.0 Hz, 1H, H23a, NCH P), 4.94 (d, J = 16.0 Hz, 1H, H21a,
2
2
ImXPad S1400 detector with a pixel size of 130.0 × 130.0 μm . The
NCH
2
N), 4.70−4.64 (m, 2H, H17a, NCH
2
P, + H21b, NCH
P), 4.06 (d, J = 20.0 Hz,
P), 3.57 (dt, J = 20.0 Hz, J
2
N), 4.15
exposure time was 10 s. The q-axis calibration was obtained by
(dt, J = 20.0 Hz, J = 4.0 Hz, 1H, H17b, NCH
1H, H19b, NCH
= 4.0 Hz, 1H, H23b, NCH
2
26
27
measuring silver behenate. The program pyFAI was used to
integrate the 2D SAXS data into 1D data.
2
N), 3.87 (s, 2H, H24, NCH
2
−1
P), 2.17 (s, 6H, COCH ). IR (KBr, cm ):
2
3
The data were then subtracted by the background using PRIMUS
3425 (C−H), 2104 (CC), 1640 (CN). ESI-MS(+): m/z 606.132
28
+
+
software. The maximum particle dimension Dmax and the pair-
([M + H] ; calcd m/z 606.133), 1233.233 ([2M + Na] ; calcd m/z
1233.241).
2
9
distance distribution function P(r) were determined with GNOM.
The low-resolution structure of the aggregates was reconstructed ab
initio from the initial portions of the scattering patterns using the
Computational Details. All quantum-level calculations were
31
performed with the Amsterdam Density Functional (ADF) program
3
0
program DAMMIN.
using the dispersion-corrected density functional ZORA-BLYP-D3-
Solutions of 1 × 10 and 1 × 10−5 M of complexes 1a, 1b, 2a, and
b were prepared in different H O/dimethyl sulfoxide (DMSO)
−4
32
(BJ). A previous benchmark study on noncovalent interactions
33
2
showed that it is essential to incorporate the dispersion correction.
2
mixtures of 0% H O to 100% (0, 25, 50, 75, and 90%) DMSO.
Geometry optimizations of monomers and dimers were obtained with
the TZ2P basis set. Geometry optimizations of tetramers were
obtained with the TZP basis set, and the bond energies were
computed with the TZ2P basis set (single point with the optimized
structures). The small frozen-core approximation was applied.
2
Synthesis of [Au(CCC H N )(PTA)] (1a). Solid PTA (21 mg,
1
5 10 3
0
.13 mmol) was added to a suspension of [Au(CCC H N )] (60
15
10
3
n
mg, 0.13 mmol) in CH Cl (20 mL). After 45 min of stirring at room
2 2
temperature, the resulting pale-yellow solution was concentrated (5
mL), and n-hexane (15 mL) was added to precipitate a pale-yellow
solid (66 mg, 81%). 31P NMR (161.9 MHz, CDCl , ppm): −12.8. H
1
O and DMSO were
3
2
34
NMR (400 MHz, CDCl , 298 K, ppm): 8.62 (dq, J = 4.8 Hz, J = 0.8
estimated using the conductor-like screening model (COSMO), as
3
3
5,36
Hz, 2H, H ), 8.53 (dt, J = 12.0 Hz, J = 1.2 Hz, 2H, H ), 8.46 (s, 2H,
implemented in the ADF program.
According to work by Riley et
9
12
3
7
H + H ), 7.84 (td, J = 11.9 Hz, J = 1.4 Hz, 2H, H ), 7.30 (ddd, J =
al., the dispersion correction does not need to be modified for
solvated systems. The bond energy ΔEbond of the dimers and tetramers
is defined by eqs 1 and 2, respectively:
3
5
11
1
2.0 Hz, J = 4.8 Hz, 2H, H ), 4.60−4.48 (AB q, J = 13.0 Hz, 6H,
10
−1
NCH N), 4.30 (s, 6H, NCH P). IR (KBr, cm ): 3425 (C−H), 2114
2
2
+
+
(
CC), 1636 (CN). ESI-MS(+): m/z 611.137 ([M + H ] ; calcd
+
+
a
b
m/z 611.139), 1243.250 ([2M + Na ] ; calcd m/z 1243.252).
Synthesis of [Au(CCC H N )(DAPTA)] (1b). Solid DAPTA (30
n
Table 1. Au−Au Distances (Å) and Bond Energies (kcal/
1
5
10
3
mol) of the Tetramers of 1a, 1b, 2a, and 2b in H O
2
mg, 0.13 mmol) was added to a suspension of [Au(CCC H N )]
15
10
3
(60 mg, 0.13 mmol) in CH Cl (20 mL). After 45 min of stirring at
Compound 1a
2
2
room temperature, the resulting pale-yellow solution was concentrated
stacked, C2h
double dimer, C2h
chain, C2
(
10 mL), and n-hexane (10 mL) was added to precipitate a pale-yellow
31
1
Au1−Au2
Au2−Au3
Au3−Au4
ΔEbond
5.99
3.27
4.13
solid (75 mg, 85%). P NMR (161.9 MHz, CDCl , ppm): −10.2. H
NMR (400 MHz, CDCl , ppm): 8.68 (dq, J = 5.0 Hz, J = 0.8 Hz, 2H,
3
10.44
5.99
11.59
3.27
3.16
3
4.13
H ), 8.56 (dt, J = 12.0 Hz, J = 0.8 Hz, 2H, H ), 8.48 (s, 2H, H + H ),
9
12
3
5
7
4
=
.82 (td, J = 11.8 Hz, J = 1.6 Hz, 2H, H ), 7.30 (ddd, J = 12.0 Hz, J =
−56.8
−41.8
−65.0
11
.8 Hz, 2H, H ), 5.78 (d, J = 20.0 Hz, 1H, H , NCH N), 5.66 (dd, J
Compound 2a
10
19a
2
20.0 Hz, J = 12.0 Hz, 1H, H23a, NCH P), 4.94 (d, J = 16.0 Hz, 1H,
2
stacked, C2h
double dimer, C1
chain, C1
H21a, NCH N), 4.70−4.64 (m, 2H, H , NCH P, + H , NCH N),
2
17a
2
21b
2
Au1−Au2
Au2−Au3
Au3−Au4
ΔEbond
5.96
3.29
3.07
4
.15 (dt, J = 20.0 Hz, J = 4.0 Hz, 1H, H1 , NCH P), 4.06 (d, J = 20.0
7b 2
11.10
5.96
6.97
3.00
Hz, 1H, H19b, NCH N), 3.87 (s, 2H, H , NCH P), 3.57 (dt, J = 20.0/
2
24
2
−1
3.28
3.10
4
3
.0 Hz, 1H, H23b, NCH P), 2.17 (s, 6H, COCH ). IR (KBr, cm ):
2
3
441 (C−H), 2116 (CC), 1640 (CN). ESI-MS(+): m/z 683.158
−57.9
−42.0
−67.6
+
+
(
[M + H] ; calcd m/z 683.160), 705.139 ([M + Na] ; calcd m/z
Compound 1b
7
05.142).
stacked, Ci
double dimer, C2
chain, C1
Synthesis of [Au(CCC H N )(PTA)] (2a). Solid PTA (25 mg,
1
0 7 2
Au1−Au2
Au2−Au3
Au3−Au4
ΔEbond
9.73
3.26
3.18
0
.16 mmol) was added to a suspension of [Au(CCC H N )] (60
10
7
2
n
6.77
11.48
3.26
3.13
mg, 0.16 mmol) in CH Cl (20 mL). After 45 min of stirring at room
temperature, the resulting yellow solution was concentrated (10 mL),
2
2
9.73
3.16
and n-hexane (10 mL) was added to precipitate a pale-yellow solid (77
−60.2
−42.5
−81.4
mg, 90%). 31P NMR (161.9 MHz, CDCl , ppm): −48.2. H NMR
1
Compound 2b
3
(
400 MHz, CDCl , ppm): 8.73 (d, J = 5.0 Hz, 1H, H ), 8.65 (dd, J =
3
9
stacked, Ci
double dimer, Ci
chain, C1
1
2.0 Hz, J = 0.8 Hz, 1H, H ), 8.36 (dt, J = 12.0 Hz, J = 4.8 Hz, 1H,
6
Au1−Au2
Au2−Au3
Au3−Au4
ΔEbond
9.64
3.59
3.22
H ), 8.29 (dd, J = 8.4 Hz, J = 2.5 Hz, 1H, H ), 7.80 (m, J = 8.0 Hz, J =
12
3
12.35
9.64
11.46
3.59
3.07
1
1
6
.6 Hz, 2H, H + H ), 7.27 (ddd, J = 8.0 Hz, J = 4.0 Hz, J = 2.0 Hz,
4 11
3.23
H, H ), 4.60−4.48 (AB q, J = 13.0 Hz, 6H, H , NCH N), 4.30 (s,
10
19b
2
−
1
H, NCH P). IR (KBr, cm ): 3425 (C−H), 2104 (CC), 1640
−56.1
−36.0
−70.0
2
+
+
(
CN). ESI-MS(+): m/z 534.111 ([M + H ] ; calcd m/z 534.112),
+
+
a
5
56.092 ([M + Na ] ; calcd m/z 556.094).
Structures of tetramers computed at the ZORA-BLYP-D3(BJ)/TZP
Synthesis of [Au(CC−C H N )(DAPTA)] (2b). Solid DAPTA (36
level of theory with the COSMO approximation for the solvent
1
0 7 2
b
mg, 0.16 mmol) was added to a suspension of [Au(CCC H N )]
(H O). Bond energies computed at the ZORA-BLYP-D3(BJ)/TZ2P
10
7
2
n
2
(
60 mg, 0.16 mmol) in CH Cl (20 mL). After 45 min of stirring at
level of theory with the COSMO approximation for the solvent
2
2
room temperature, the resulting yellow solution was concentrated (10
(H O).
2
C
Inorg. Chem. XXXX, XXX, XXX−XXX