Metal complexes of N-m-nitrobenzenesulfonylamido-meso-tetraphenyl porphyrin: M(N-NSO2(m-NO2)C6H4-tpp) (M = Zn2+, Ni2+, Cu2+) and Tl(N-NSO2(m-NO2)C6H4-tpp)(OAc) (tpp = 5, 10, 15, 20-tetraphenyl porphyrinate)

Article abstract of DOI:10.1016/j.poly.2009.12.019

The crystal structures of N-m-nitrobenzenesulfonylimido-meso-tetraphenylporphyrinatonickel(II) [Ni(N-NSO₂(m-NO₂)C₆H₄tpp); 3], N-m-nitrobenzenesulfonylimido-meso-tetraphenylporphyrinatocopper(II) [Cu(N-NSO₂(m-NO₂)C₆H₄tpp); 4], N-m-nitrobenzenesulfonylimido-meso-tetraphenylporphyrinatozinc(II) chloroform solvate [Zn(N-NSO₂(m-NO₂)C₆H₄tpp)·CHCl₃; 5·CHCl₃] and cis-acetato-N-m-nitrobenzenesulfonylimido-meso-tetraphenylporphyrinatothallium(III) chloroform solvate [Tl(N-NSO₂(m-NO₂)C₆H₄tpp)(OAc)·CHCl₃; 6·CHCl₃] have been established. The coordination sphere around the Zn²⁺ ion in 5·CHCl₃ (or Cu²⁺ ion in 4) is distorted square planar (DSP), and for the Tl³⁺ ion in 6·CHCl₃, it is a distorted trigonal prism (DTPR). The ion-dipole interaction between the Ni²⁺ ion and the nitroaryl group dipole enforces that Ni²⁺ in 3 preserves a distorted square planar pattern, but in addition the NO₂ moiety of the N-substituent is in close contact at the apical site.

Full text of DOI:10.1016/j.poly.2009.12.019

Polyhedron 29 (2010) 1116–1122
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Metal complexes of N-m-nitrobenzenesulfonylamido-meso-tetraphenyl porphyrin:
M(N-NSO2(m-NO2)C6H4-tpp) (M = Zn2+, Ni2+, Cu2+) and Tl(N-NSO2(m-NO2)C6H4-
tpp)(OAc) (tpp = 5, 10, 15, 20-tetraphenyl porphyrinate)
b
c,
Cheng-Hsiung Cho a, Cheng-Chun Peng a, Jyh-Horung Chen a, , Shin-Shin Wang , Jo-Yu Tung
*
*
a Department of Chemistry, National Chung Hsing University, Taichung 40227, Taiwan
b Material Chemical Laboratories ITRI, Hsin-Chu 300, Taiwan
c Department of Occupational Safety and Health, Chung Hwai University of Medical Technology, Taiwan
a r t i c l e i n f o
a b s t r a c t
Article history:
The crystal structures of N-m-nitrobenzenesulfonylimido-meso-tetraphenylporphyrinatonickel(II) [Ni(N-
NSO2(m-NO2)C6H4tpp); 3], N-m-nitrobenzenesulfonylimido-meso-tetraphenylporphyrinatocopper(II)
[Cu(N-NSO2(m-NO2)C6H4tpp); 4], N-m-nitrobenzenesulfonylimido-meso-tetraphenylporphyrinatozinc(II)
chloroform solvate [Zn(N-NSO2(m-NO2)C6H4tpp)ꢀCHCl3; 5ꢀCHCl3] and cis-acetato-N-m-nitrobenzenesulf-
onylimido-meso-tetraphenylporphyrinatothallium(III) chloroform solvate [Tl(N-NSO2(m-NO2)C6H4tp-
p)(OAc)ꢀCHCl3; 6ꢀCHCl3] have been established. The coordination sphere around the Zn2+ ion in 5ꢀCHCl3
(or Cu2+ ion in 4) is distorted square planar (DSP), and for the Tl3+ ion in 6ꢀCHCl3, it is a distorted trigonal
prism (DTPR). The ion-dipole interaction between the Ni2+ ion and the nitroaryl group dipole enforces
that Ni2+ in 3 preserves a distorted square planar pattern, but in addition the NO2 moiety of the N-sub-
stituent is in close contact at the apical site.
Received 11 November 2009
Accepted 2 December 2009
Available online 21 December 2009
Keywords:
Nickel porphyrin
Ion–dipole forces
Crystal structures
Distorted trigonal prism
Ó 2009 Elsevier Ltd. All rights reserved.
1. Introduction
ion preserves the pattern of equatorial coordination, but in addi-
tion the nitrogen dioxide, NO2, moiety of the N-substituent is in
Recently, we reported on the strong and attractive electrostatic
interaction between M3+ (M = Ga, Mn) and Oꢁ of the N-o-oxido
benzimido-meso-tetraphenylporphyrinato [N-NCO(o-O)C6H4-tpp;
1] ligand, stabilized by the five coordinate gallium Ga(N-NCO(o-
O)C6H4tpp) and manganese complex Mn(N-NCO(o-O)C6H4tpp)
[1]. In this paper, we report the extension of the electrostatic inter-
action between a metal cation and a ligand anion to an ion–dipole
attractive interaction between a metal cation and the molecular di-
pole of a ligand [2]. Hence the new free amidated porphyrin,
namely N-m-nitrobenzenesulfonylamido-meso-tetraphenyl por-
phyrin [N-NHSO2(m-NO2)C6H4-Htpp, 2] (Scheme 1) was synthe-
sized, which is an N-substituted porphyrin [3].
close contact in the apical position (Scheme 1).
The lack of a study on metal complexes of ligand 2 prompted us
to undertake the synthesis and structural investigations of the
nickel(II), zinc(II), copper(II) and thallium(III) complexes. In this
paper, we describe the X-ray structural investigation on the metal-
lation of 2 leading to the nickel complex N-m-nitrobezenesulf-
onylimido-meso-tetraphenylporphyrinatonickel(II) [Ni(N-NSO2(m-
NO2)C6H4tpp); 3], the copper complex N-m-nitrobezenesulfony-
limido-meso-tetraphenylporphyrinatocopper(II)
[Cu(N-NSO2(m-
NO2)C6H4tpp); 4], the zinc complex N-m-nitrobezenesulfonylimi-
do-meso-tetraphenylporphyrinatozinc(II) chloroform solvate [Zn-
(N-NSO2(m-NO2)C6H4tpp)ꢀCHCl3; 5ꢀCHCl3] and the thallium com-
plex cis-acetato-N-m-nitrobezenesulfonylimido-meso-tetraphenyl-
porphyrinatothallium(III) chloroform solvate [Tl(N-NSO2(m-NO2)-
C6H4tpp)(OAc)ꢀCHCl3; 6ꢀCHCl3]. Furthermore, in this study we try
to figure out why the configuration around Ni2+ in 3 is definitely
different from that of Cu2+ in 4, Zn2+ in 5ꢀCHCl3 and Tl3+ in 6ꢀCHCl3.
Nitrogen dioxide, NO2, of the NSO2(m-NO2)C6H4 ligand in 2 can
be considered to be a group dipole if the two resonance structures
(a) and (b) given in Scheme 2 are considered to be the most impor-
tant forms [4].
Depending on the metal ion choice, two principal structural
motifs have been detected. In the first case [Tl3+, Zn2+ and Cu2+
]
the N-substituted porphyrin acts as a tetradentate macrocycle,
2. Experimental
using three pyrrolic and one amidate nitrogen. The divalent Ni2+
2.1. N-NHSO2(m-NO2)C6H4-Htpp (2)
* Corresponding authors. Tel.: +88 64 228 40411x612; fax: +88 64 228 62547 (J.-
H. Chen), tel.: +88 66 267 4567x815; fax: +88 66 289 4028 (J.-Y. Tung).
E-mail addresses: JyhHChen@dragon.nchu.edu.tw (J.-H. Chen), joyuting@mail.
hwai.edu.tw (J.-Y. Tung).
The purple solid of 2 was prepared in 44% yield in the same way
as described for N-p-HNSO2C6H4 tBu-Htpp, but using 3-nitroben-
zene-1-sulfonyl chloride with a reaction time of 3 h [5].
0277-5387/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2009.12.019

C.-H. Cho et al. / Polyhedron 29 (2010) 1116–1122
1117
O-
O
C
N
N-
-N
N
N
(1)
NO2
NO2
4
4
2
2
3
5
5
O
S
O
S
1
O
O
1
6
6
Ph
Ph
Ph
Ph
Ph
Ph
N
N
N
HN
Y
M(OAc)n .x H2O
N
M
N
N
NH
N
N
CH2Cl2/MeOH, reflux m h
Ph
Ph
(2)
M = Cu2+ ; n = 2 ; x=1 ; m=12; Y=empty (4); 57%
= Zn2+ ; n = 2 ; x=2 ; m=3; Y=empty (5); 57%
= Tl3+ ; n = 3 ; x=0; m=3; Y=OAc- (6); 47%
NO2
5
4
6
O
O
S
N
O
O
S
1
O
2
O
Ph
Ph
Ph
Ph
Ph
N
N
N
N
HN
.
Ni(OAc)2 4 H2O
N
NH
N
Ni
N
MeCN, reflux 6 h
N
Ph
Ph
Ph
(2)
(3) ; 57%
Scheme 1.
2.2. Zn(N-NSO2(m-NO2)C6H4tpp)ꢀCHCl3 (5ꢀCHCl3)
for single-crystal X-ray analysis. 1H NMR (599.95 MHz, CDCl3,
20 °C): d 8.91 [d, Hb(2, 13), 3J(H–H) = 4.8 Hz], 8.89 [d, Hb(3, 12),
3J(H–H) = 4.8 Hz], 8.87 [s, Hb(7, 8)], 7.52 [s, Hb(17, 18)], 8.48 [d,
o-H (26, 28), 3J(H–H) = 7.2 Hz], 8.08 [d, o-H (22, 32), 3J(H–
H) = 7.2 Hz] where o-H = phenyl ortho protons, 7.92(s) and
8.28(s) for o0-H (34, 44) and o0-H (38, 40), 7.72–7.91 (broad) for
phenyl meta and para protons (m-, p-H), 7.94 [s, H(48) or (m-
NO2)BSA-Ph-H4], where (m-NO2)BSA = the m-nitrobenzenesulf-
onylamido ligand, 6.99 [t, H(49), 3J(H–H) = 7.8 Hz], 6.36 [s,
H(50)], 5.89 [d, H(46), 3J(H–H) = 7.8 Hz]. MS (FAB): (M)+ 877 (calcd
A mixture of 2 (0.057 g, 0.070 mmol) in CH2Cl2 (20 cm3) and
Zn(OAc)2ꢀ2H2O (0.05 g, 0.228 mmol) in MeOH (3 cm3) was refluxed
at 60 °C for 3 h. After concentration, the residue was dissolved in
CH2Cl2, dried with anhydrous Na2SO4 and filtered. The filtrate
was concentrated and dissolved in CDCl3 for 1H NMR measurement
in order to identify the crude product of 5. After that, the solution
was again concentrated yielding a purple solid, which was again
dissolved in CH2Cl2 and layered with MeOH to get the purple solid
of 5ꢀCHCl3 (0.035 g, 0.040 mmol, 57%). Compound 5ꢀCHCl3 was dis-
solved in CH2Cl2 and layered with MeOH to afford purple crystals
for C50H32N6O4SZn: 878). UV/visible [k, nm (10ꢁ3
e
, Mꢁ1 cmꢁ1)] in
CH2Cl2: 722 (8.11), 603 (19.3), 437 (236), 381 (24.8).

1118
C.-H. Cho et al. / Polyhedron 29 (2010) 1116–1122
Cu(OAc)2ꢀH2O with a reaction time of 12 h. Compound 4 was dis-
O
O
O
O
S
O
S
O
S
solved in CH2Cl2 and layered with MeOH to afford a purple crystals
for single-crystal X-ray analysis. MS (FAB): (M)+ 876 (calcd for
O
C50H32N6O4SCu: 876). UV/visible [k, nm (10ꢁ3 , Mꢁ1 cmꢁ1)] in
e
CH2Cl2: 592 (3.39), 431 (60.4).
N
N
N
O
O
O
O
O
2.5. Tl(N-NSO2(m-NO2)C6H4tpp)(OAc))ꢀCHCl3 (6ꢀCHCl3)
(c)
(b)
(a)
A mixture of 2 (0.057 g, 0.070 mmol) in CH2Cl2 (20 cm3) and
Tl(OAc)3 (0.050 g, 0.131 mmol) in MeOH (3 cm3) was refluxed at
60 °C for 3 h. After concentrating, the residue was dissolved in a
suitable amount of CH2Cl2, dried over anhydrous Na2SO4 and fil-
tered. The filtrate was concentrated and dissolved in CDCl3 for 1H
NMR measurement in order to identify the crude product of 6.
After that the solution was again concentrated yielding the pure
solid, which was again dissolved in CH2Cl2 and layered with MeOH
[CH2Cl2:MeOH = 1:2 (v/v)] to get the purple solid of 6 (0.035 g,
0.033 mmol, 47%). Compound 6 was redissolved in CH2Cl2 and lay-
ered with MeOH to afford purple crystals for single-crystal X-ray
analysis. 1H NMR (599.95 MHz, CDCl3, 20 °C) d 9.03 [d, Hb(2, 13),
4J(Tl–H) = 13.2 Hz], 8.99 [s, Hb(3, 12)], 8.84 [d, Hb(7, 8), 4J(Tl–
H) = 84.6 Hz], 7.04 [s, Hb(17, 18)], 8.49 [d, o-H (26, 28), 3J(H–
H) = 7.2 Hz], 8.09 [d, o-H (22, 32), 3J(H–H) = 7.8 Hz], 7.76–7.85
(m, m-, p-H), 8.07 [s, H(48)], 7.76[s, H(46)], 7.04 [t, H(49),
3J = 15 Hz], 5.71 [d, H(50), 3J(H–H) = 7.8 Hz], 0.79 (s, OAc). MS
(FAB): (M)+ 1076 (calcd for C52H35N6O6STl: 1076). UV/visible [k,
O
O
S
O
S
O
......
N
N
O
O
O
O
(e)
(d)
Scheme 2.
2.3. Ni(N-NSO2(m-NO2)C6H4tpp) (3)
Compound 3 was prepared in 57% yield in the same way as de-
scribed for Zn(N-NSO2(m-NO2)C6H4tpp)ꢀCHCl3 (5ꢀCHCl3), using
Ni(OAc)2ꢀ4H2O and MeCN with a reaction time of 6 h. Compound
3 was dissolved in CH2Cl2 and layered with MeOH to afford purple
crystals for single-crystal X-ray analysis. 1H NMR (599.95 MHz,
CDCl3, 20 °C): d 8.79 [s, Hb(7, 8)], 8.64 [s, Hb(3, 12) and Hb(2, 13)],
7.39 [s, Hb(17, 18)], 7.84 [d, 3J(H–H) = 7.2 Hz] and 8.37 [d, 3J(H–
H) = 7.2 Hz] for o-H(22, 32) and o-H(26, 28), 8.41(s) and 7.61(s)
for o0-H(34, 44) and o0-H(38, 40), 7.61–7.86 (broad, m-, p-H), 7.78
[s, H(48)], 6.94 [ t, H(49), 3J(H–H) = 7.8 Hz], 6.08 [d, H(50), 3J(H–
H) = 7.8 Hz], 6.01 [s, H(46) or (m-NO2)BSA-Ph-H2]. MS (FAB): (M)+
nm (10ꢁ3 , Mꢁ1 cmꢁ1)] in CH2Cl2: 718 (8.1), 612 (18.1), 447 (196).
e
2.6. Spectroscopy
ESR spectra were measured on an X-band Bruker EMX-10
spectrometer equipped with an Oxford Instruments liquid helium
cryostat. Magnetic field values were measured with a digital
counter. The X-band resonator was a dual-mode cavity (Bruker
ER 4116 DM). Proton and 13C NMR spectra were recorded at
599.95 and 150.87 MHz, respectively, on Varian Unity Inova-600
spectrometers locked on deuterated solvent and referenced to
the solvent peak. The proton NMR spectra are relative to CD2Cl2
or CDCl3 at d = 5.30 or 7.24 and 13C NMR spectra to the center line
of CD2Cl2 or CDCl3 at d = 53.6 or 77.0. Nuclear Overhauser effect
871 (calcd for C50H32N6O4SNi: 871). UV/visible [k, nm (10ꢁ3
ꢁ1 cmꢁ1)] in CH2Cl2: 580 (13.9), 425 (157), 310 (29.2).
e,
M
2.4. Cu(N-NSO2(m-NO2)C6H4tpp) (4)
Compound 4 was prepared in 57% yield in the same way as de-
scribed for Zn(N-NSO2(m-NO2)C6H4tpp)ꢀCHCl3 (5ꢀCHCl3) using
Table 1
Crystal data for 3, 4, 5ꢀCHCl3 and 6ꢀCHCl3.
Compound
(3)
(4)
(5ꢀCHCl3)
(6ꢀCHCl3)
Empirical formula
Formula weight
Space group
Crystal system
a (Å)
C50H32N6NiO4S
871.59
P21/c
monoclinic
13.0566(18)
13.1219(18)
23.924(3)
90
C50H32CuN6O4S
876.42
P21/c
monoclinic
9.8859(2)
19.5726(5)
23.572(6)
90
C51H33Cl3N6O4SZn
997.61
P21/c
monoclinic
10.0997(7)
19.7235(13)
23.7667(17)
90
C53H36Cl3N6O6STl
1195.66
P21/c
monoclinic
15.0346(2)
21.2948(4)
15.8173(3)
90
b (Å)
c (Å)
a
(°)
b (°)
91.060(2)
90
4098.1(10)
4
99.483(2)
90
4499.87(19)
4
100.0390(10)
90
4661.9(6)
4
104.0270(10)
90
4913.04(15)
4
c
(°)
V (Å3)
Z
F(0 0 0)
1800
1.413
0.580
1804
1.294
0.583
2040
1.421
0.796
2368
1.616
3.551
Dcalcd (g cmꢁ3
)
l(Mo K
a
), (mmꢁ1
)
S
1.057
1.067
1.348
1.114
Crystal size (mm)
h (°)
0.40 ꢂ 0.30 ꢂ 0.30
0.54 ꢂ 0.16 ꢂ 0.14
0.20 ꢂ 0.15 ꢂ 0.10
0.32 ꢂ 0.24 ꢂ 0.20
28.32
26.00
26.04
25.37
T (K)
100(2)
100(2)
297(2)
200(2)
Number of reflections measured
Number of reflections observed
10 196
7771
0.0472
0.1186
10 740
7071
0.0722
0.2041
9163
5199
0.0934
0.2500
8868
7402
0.0578
0.1564
a
R1
b
wR2
P
P
a
R1 ¼ ½ kFoj ꢁ jFck= jFojꢃ.
P
P
2
2 1=2
wR2 ¼ ½ wðF2o ꢁ Fc2Þ = wðF2oÞ ꢃ
.
b

C.-H. Cho et al. / Polyhedron 29 (2010) 1116–1122
1119
Table 2
200(2) K for 6ꢀCHCl3-(Tl). Empirical absorption corrections were
made for complexes 3-(Ni) and 5ꢀCHCl3-(Zn), and semi-empirical
absorption corrections were made for 4-(Cu) and 6ꢀCHCl3-(Tl).
The structures were solved by direct methods (SHELXL-97) [6] and
refined by the full-matrix least-squares methods. The Cu atom
and phenyl group C(33)–C(38) within 4-(Cu) are disordered with
an occupancy factor of 0.39 for C(33)–C(38) and 0.61 for
C(330)–C(380), 0.92 for Cu and 0.08 for Cu0. The solvent CHCl3 and
phenyl group C(39)–C(44) within 5ꢀCHCl3–(Zn) are disordered with
an occupancy factor of 0.5 for C(39)–C(44) and 0.5 for
C(390)–C(440), 0.43 for Cl(1) and 0.57 for Cl(10), 0.42 for Cl(2) and
0.58 for Cl(20), 0.26 for Cl(3) and 0.74 for Cl(30). All non-hydrogen
atoms were refined with anisotropic thermal parameters,
whereas all hydrogen atoms were placed in calculated positions
and refined with a riding model. Table 2 lists selected bond dis-
tances and angles for complexes 3-(Ni), 4-(Cu), 5ꢀCHCl3–(Zn) and
6ꢀCHCl3–(Tl).
Selected bond distances (Å) and angles (°) for compounds 3, 4, 5ꢀCHCl3 and 6ꢀCHCl3.
Compound 3
Bond lengths (Å)
Ni(1)–N(1)
Ni(1)–N(2)
Ni(1)–N(3)
1.924(2)
1.872(2)
1.925(2)
Ni(1)–N(5)
1.829(2)
Bond angles (°)
N(1)–Ni(1)–N(2)
N(1)–Ni(1)–N(3)
N(1)–Ni(1)–N(5)
N(2)–Ni(1)–N(3)
N(2)–Ni(1)–N(5)
N(3)–Ni(1)–N(5)
94.67(7)
167.35(7)
86.61(8)
94.15(8)
164.52(8)
87.31(8)
S(1)–N(5)–Ni(1)
N(4)–N(5)–Ni(1)
117.4(1)
113.6(1)
Compound 4
Bond lengths (Å)
Cu–N(1)
Cu–N(2)
Cu–N(3)
2.018(3)
1.897(3)
2.009(4)
Cu–N(5)
1.900(3)
Bond angles (°)
N(1)–Cu–N(2)
N(1)–Cu–N(3)
N(1)–Cu–N(5)
N(2)–Cu–N(3)
N(2)–Cu–N(5)
N(3)–Cu–N(5)
94.1(1)
161.1(1)
88.6(1)
94.2(1)
160.5(2)
89.1(2)
S–N(5)–Cu
N(4)–N(5)–Cu
137.8(2)
105.0(2)
3. Results and discussion
3.1. Structures of 3-(Ni), 4-(Cu), 5ꢀCHCl3–(Zn), 6ꢀCHCl3–(Tl)
The complexation of Cu2+ and Zn2+, classified as divalent B acids,
with 2 forms four-coordinate copper(II) (4) and Zn(II) (5) com-
plexes (Scheme 1) [7,8]. The complexation of Tl3+, classified as a tri-
valent C acid, with 2 forms a six-coordinate Tl(III) (6) complex
[7,8]. The X-ray framework is depicted in Fig. 1 for complexes 3-
(Ni) and 4-(Cu), and in Fig. 2 for complexes 5ꢀCHCl3–(Zn) and
6ꢀCHCl3–(Tl) (Figs. S1 and S2 in Supplementary data). All these
structures, four-coordinate distorted square-planar (DSP) nickel
of 3 (or copper of 4, zinc of 5ꢀCHCl3) and six-coordinate thallium
of 6ꢀCHCl3–(Tl), show bonding with three nitrogen atoms of the
porphyrin and one extra nitrogen atom of the nitrene fragment
in common, but compound 6ꢀCHCl3–(Tl) has, in addition, one
bidentate OAcꢁ ligand in the axial site. The metal–ligand distances
and angles are summarized in Table 2. The distance between M
(M = Ni2+, Cu2+, Zn2+ and Tl3+) and O(4) increases from 5.632 Å
for Ni2+, to 7.960 Å for Cu2+, 8.064 Å for Zn2+ and to 8.197 Å for
Tl3+ (Table 3). Specifically, Ni2+, with a coordination number (CN)
of 4 and a higher Z value of 1.474, is a divalent E acid.1 A strong
and attractive ion-dipole interaction between Ni2+ and the nitroaryl
group dipole rotates the (m-NO2)BSA ligand along the S(1)–C(45)
bond in 3 and finally stabilizes the four-coordinate nickel(II) com-
plex 3 with a closer contact at a distance of 5.632 Å between Ni(1)
and O(4).
Compound 5ꢀCHCl3
Bond lengths (Å)
Zn(1)–N(1)
Zn(1)–N(2)
Zn(1)–N(3)
2.068(5)
1.915(5)
2.058(4)
Zn(1)–N(5)
1.973(5)
Bond angles (°)
N(1)–Zn(1)–N(2)
N(1)–Zn(1)–N(3)
N(1)–Zn(1)–N(5)
N(2)–Zn(1)–N(3)
N(2)–Zn(1)–N(5)
N(3)–Zn(1)–N(5)
95.0(2)
161.2(2)
89.8(2)
94.7(2)
149.6(2)
90.0(2)
S(2)–N(5)–Zn(1)
N(4)–N(5)–Zn(1)
147.1(3)
95.8(4)
Compound 6ꢀCHCl3
Bond lengths (Å)
Tl(1)–N(1)
Tl(1)–N(2)
Tl(1)–N(3)
2.392(7)
2.151(8)
2.338(8)
Tl(1)–N(5)
Tl(1)–O(3)
Tl(1)–O(4)
2.140(7)
2.348(7)
2.360(8)
Bond angles (°)
N(1)–Tl(1)–N(2)
N(1)–Tl(1)–N(3)
N(1)–Tl(1)–N(5)
N(2)–Tl(1)–N(3)
N(2)–Tl(1)–N(5)
N(3)–Tl(1)–N(5)
O(3)–Tl(1)–N(1)
O(3)–Tl(1)–N(2)
O(3)–Tl(1)–N(3)
O(3)–Tl(1)–N(5)
79.8(3)
116.3(3)
81.6(3)
81.3(3)
148.7(3)
84.8(3)
152.3(3)
99.1(3)
90.5(3)
109.0(3)
S(1)–N(5)–Tl(1)
N(4)–N(5)–Tl(1)
O(3)–Tl(1)–O(4)
O(4)–Tl(1)–N(1)
O(4)–Tl(1)–N(2)
O(4)–Tl(1)–N(3)
O(4)–Tl(1)–N(5)
131.3(4)
111.7(5)
55.4(3)
98.0(3)
105.9(3)
145.6(3)
101.4(3)
It is noted that the ionic radius increases from 0.63 Å for Ni2+
,
0.71 Å for Cu2+, 0.74 Å for Zn2+ to 1.025 Å for Tl3+ [9]. Because of
the larger size of Tl3+, Tl3+ lies 1.20 Å above the 3N plane in 6, com-
pared to 0.25 Å for Zn2+ in 5, 0.27 Å for Cu2+ in 4 and 0.14 Å for Ni2+
in 3 (Table 3). We adopt the plane of the three strongly bound pyr-
role nitrogen atoms [i.e. N(1), N(2) and N(3)] as a reference plane
3N for 3, 4, 5 and 6. The porphyrin macrocycle is indeed distorted
because of the presence of the (m-NO2)BSA group. The N(4) pyrrole
rings bearing the (m-NO2)BSA group in 3–6 deviate mostly from
the 3N plane, orienting separately with a dihedral angle of
42.7°(or 37.5°, 30.3°, 49.5°) for 3, (or 4, 5, 6) (Table 3).
(NOE) difference spectroscopy was employed to determine the
1H–1H proximity through space over a distance of up to about
4 Å.
The positive-ion fast atom bombardment mass spectra (FAB
MS) were obtained in a nitrobenzyl alcohol (NBA) matrix using a
JEOL JMS-SX/SX 102A mass spectrometer. UV/visible spectra were
recorded at 20 °C on a HITACHI U-3210 spectrophotometer.
3.2. 1H NMR spectroscopy data of 3, 5ꢀCHCl3–(Zn), 6ꢀCHCl3–(Tl) in
2.7. X-ray crystallography
CDCl3
Table 1 presents the crystal data as well as other information for
3-(Ni), 4-(Cu), 5ꢀCHCl3-(Zn) and 6ꢀCHCl3-(Tl). Measurements were
taken on a Bruker AXS SMART-1000 diffractometer using mono-
Due to the ring current effect, the upfield shifts for the 1H reso-
nances of (m-NO2)BSA-Ph-H6, (m-NO2) BSA-Ph-H2, (m-NO2)BSA-
1
chromatized Mo Ka radiation (k = 0.71073 Å) at a temperature of
Substituting rion = 0.63 Å into Zhang’s scale for the Lewis acid strength, the Z value
100(2) K for 3-(Ni) and 4-(Cu) and 297(2) K for 5ꢀCHCl3-(Zn) and
for Ni2+ changes from 0.293 to 1.474 [7]. Hence Ni2+ becomes a divalent E acid.

1120
C.-H. Cho et al. / Polyhedron 29 (2010) 1116–1122
Fig. 2. Molecular configuration and atom-labeling scheme for (a) 5ꢀCHCl3 and (b)
6ꢀCHCl3, with 30% thermal ellipsoids. Hydrogen atoms and solvent CHCl3 are
omitted for clarity.
Fig. 1. Molecular configuration and atom-labeling scheme for (a) 3 and (b) 4, with
30% thermal ellipsoids. Hydrogen atoms are omitted for clarity.
Table 3
X-ray data and Z values for complexes 3–6.
d
Compound
rion (Å)
X-ray
Z
Classification of metal ionse [8]
–
D
(3N)a (Å)
Mꢀ ꢀ ꢀO(3)b
hc (°)
Coordinationf geometry
–
Mꢀ ꢀ ꢀO(4) (Å)
Tl3+ in 6
Zn2+ in 5
Cu2+ in 4
Ni2+ in 3
1.025
0.74
0.71
0.63
1.20
0.25
0.27
0.14
8.761
8.197
8.874
8.064
8.737
7.960
6.925
5.632
49.5
30.3
37.5
42.7
DTPR-6g
DSP-4h
DSP-4
ꢁ0.580
0.656
0.177
1.474
C
B
B
E
DSP-4
a
b
c
D
(3N) denotes the displacement of the metal center from the 3N plane.
M = Zn2+, Ni2+, Cu2+ and Tl3+
.
h: Dihedral angle between the pyrrole ring bearing a (m-NO2)BSA group and the 3N plane.
Z: Zhang’s scale for strengths of Lewis acids [8].
Electrostatic or covalent nature of Lewis acids. C acids = large covalent acids, B acids = border acids, and E acids = large electrostatic acids.
Coordination geometry is expressed by the polyhedral symbol.
DTPR = distorted trigonal prism.
DSP = distorted square-planar.
d
e
f
g
h

C.-H. Cho et al. / Polyhedron 29 (2010) 1116–1122
1121
Ph-H5 and (m-NO2)BSA-Ph-H4 for 5ꢀCHCl3–(Zn) in CDCl3 at 20 °C
are
d ¼ ꢁ2:36 [from 8.25 (obtained from 3-nitrobenzenesulfona-
SA-Ph-H6, Ctꢀ ꢀ ꢀ(m-NO2)BSA-Ph-H5 and Ctꢀ ꢀ ꢀ(m-NO2)BSA-Ph-H4 in-
creases from 3.874, 5.173, 6.688 to 6.923 Å, respectively. The
upfield shifts for the 1H resonances of (m-NO2)BSA-Ph-H2, (m-
NO2)BSA-Ph-H6, (m-NO2)BSA-Ph-H5 and (m-NO2)BSA-Ph-H4 for 3
D
mide) to 5.89 ppm], ꢁ2.24 (from 8.6 to 6.36 ppm), ꢁ0.91 (from 7.9
to 6.99 ppm) and ꢁ0.55 ppm (from 8.45 to 7.90 ppm), respectively
(Fig. 3). Qualitatively as the distance between the geometrical
center (Ct) of the 4N plane and axial protons gets smaller, the
shielding effect becomes larger [10]. In 5ꢀCHCl3–(Zn), the distance
for Ctꢀ ꢀ ꢀ(m-NO2)BSA-Ph-H6, Ctꢀ ꢀ ꢀ(m-NO2)BSA-Ph-H2, Ctꢀ ꢀ ꢀ(m-
NO2)BSA-Ph-H5, Ctꢀ ꢀ ꢀ(m-NO2)BSA-Ph-H4 increases from 3.888,
5.792, 5.962 to 7.408 Å, individually. As (m-NO2)BSA-Ph-H6 (i.e.
H50) of 5ꢀCHCl3–(Zn) is closer to Ct, the shielding is larger for
(m-NO2)BSA-Ph-H6. A similar ring current effect is also observed
for 6ꢀCHCl3–(Tl), with the resonance for the proton of (m-NO2)-
BSA-Ph-H6 (i.e. H50) being observed at d ¼ 5:86 ppm. Moreover,
in 3-(Ni), the distance of Ctꢀ ꢀ ꢀ(m-NO2)BSA-Ph-H2, Ctꢀ ꢀ ꢀ(m-NO2)B-
in CDCl3 at 20 °C are
D
d ¼ ꢁ2:59 (from 8.6 to 6.01 ppm), ꢁ2.17
(from 8.25 to 6.08 ppm), ꢁ0.96 (from 7.9 to 6.94 ppm), and
ꢁ0.67 ppm (from 8.45 to 7.78 ppm), respectively (Fig. 4). Due to
the strong intramolecular ion–dipole interaction in 3, the closest
distance between Ct and the protons of (m-NO2)BSA-Ph changes
from (m-NO2)BSA-Ph-H2 for 4, 5, 6 to (m-NO2)BSA-Ph-H6 for 3-(Ni).
3.3. ESR spectra for 4-(Cu)
Complex 4-(Cu) is paramagnetic because of the d9 configuration
of Cu(II). The unpaired electron resides in the dx2
orbital, which
ꢁy2
Fig. 3. 1H NMR spectra for 5ꢀCHCl3–(Zn) at 599.95 MHz in CDCl3 at 20 °C showing four different b-pyrrole protons Hb, phenyl protons (o-H, m, p-H) and (m-NO2)BSA-Ph
protons. Chemical shifts are in ppm from CDCl3 at 7.24 ppm.
Fig. 4. 1H NMR spectra for 3-(Ni) at 599.95 MHz in CDCl3 at 20 °C showing four different b-pyrrole protons Hb, phenyl protons (o-H, m, p-H) and (m-NO2)BSA-Ph protons.
Chemical shifts are in ppm from CDCl3 at 7.24 ppm.

1122
C.-H. Cho et al. / Polyhedron 29 (2010) 1116–1122
leads to characteristic ESR spectra for 6 in CH2Cl2 at 20 °C: four
peaks in the ESR are typical for a planar copper(II) complex due
to the nuclear spin (I = 3/2) of Cu, and a nine-line pattern is due
to the super hyperfine interactions with the four nitrogens (I = 1)
and 6ꢀCHCl3-(Tl), and their X-ray structures have been established.
The strong ion-dipole interaction between Ni2+ (E acid) and the
NO2 molecular dipole rotates the NO2 group of (m-NO2)BSA closer
to Ni2+ in 3-(Ni). This directional interaction explains why the con-
figuration around Ni2+ in 3 is different from the configurations of
Cu2+ in 4, Zn2+ in 5ꢀCHCl3 and Tl3+ in 6ꢀCHCl3.
of the porphyrin with giso = 2.06, Aiso(
63Cu) = 65.8 G and Ai-
(
so
14N) = 14.1 G for 4-(Cu) in CH2Cl2 at 20 °C and with gk ¼ 2:20
and A (63Cu) = 171.5 G for 4-(Cu) in CH2Cl2 at 77 K.
k
Acknowledgements
3.4. Dynamic NMR of 6 in CD2Cl2
The financial support from the National Science Council of the
ROC under Grant NSC 98-2113-M-005-005 is gratefully acknowl-
edged. We thank Dr. S. Elango for helpful discussions.
Upon cooling of a 0.02 M CD2Cl2 solution of 6, the methyl pro-
ton signal of OAc-, being a single peak at 20 °C (d ¼ 0:65 ppm), first
broadened (coalescence temperature Tc = 211 K) and then split into
peaks with a separation of 16.2 Hz at d ¼ 0:56 ppm at ꢁ90 °C. As
the exchange of OAcꢁ within 6 is reversible, the results at
599.95 MHz confirm the separation of a coupling of 4J(Tl–H) rather
than a chemical shift difference. The most likely cause of loss of
coupling is due to the reversible dissociation of acetate with a
small dissociation constant:
Appendix A. Supplementary data
CCDC 749634, 749635, 749636, and 749637 contain the supple-
mentary crystallographic data for 3, 4, 5ꢀCHCl3 and 6ꢀCHCl3. These
data can be obtained free of charge via http://www.ccdc.cam.ac.uk/
conts/retrieving.html, or from the Cambridge Crystallographic
Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44)
1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
TlðN-NSO2ðm-NO2ÞC6H4tppÞðOAcÞ
CD2Cl2
ꢀ
TlðN-NSO2ðm-NO2ÞC6H4tppÞþ þ OAcꢁ:
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.poly.2009.12.019.
Such a scenario could lead to the change in the chemical shift
with temperature and no detectable free OAcꢁ and Tl(N-NSO2(m-
NO2)C6H4tpp)+ at low temperature, but would lead to the loss of
coupling between acetate and thallium at high temperature [11].
The free energy of activation at the coalescence temperature Tc
for the intermolecular exchange of OAcꢁ in 6 was determined to
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be
D
Gꢄ211 ¼ 44:8 kJ=mol. At 20 °C, intermolecular exchange of the
OAcꢁ group for 6 is rapid as indicated by the appearance of singlets
due to carbonyl carbons at 176.7 ppm and methyl carbons at
19.0 ppm. At ꢁ90 °C, the rate of intermolecular exchange of OAcꢁ
for 6 in CD2Cl2 is slow. Hence at this temperature, the methyl
and carbonyl carbons of OAcꢁ are observed at 18.6 ppm with
[3J(Tl–C) = 230 Hz] and 176.8 ppm with [2J(Tl–C) = 212 Hz] as dou-
blets, respectively. These 13C resonances are quite close to those of
Tl(N-p-NCOC6H4NO2-tpp)(OAc) in which the two corresponding
carbons were observed at d 18.9 ppm [with 3J(Tl–C) = 227 Hz]
and 175.9 ppm [with 2J(Tl–C) = 211 Hz] as doublets in THF-d8 at
ꢁ110 °C [12].
4. Conclusions
We have investigated four new porphyrin metal complexes, one
paramagnetic 4-(Cu) and three diamagnetic 3-(Ni), 5ꢀCHCl3-(Zn)