Multicomponent supramolecular systems: self-organization in Coordination-Driven self-assembly

Article abstract of DOI:10.1002/chem.200900230

The self-organization of multicomponent supramolecular systems involving a variety of two-dimensional (2D) polygons and three-dimensional (3D) cages is presented. Nine self-organizing systems, SS₁-SS₉, have been studied. Each involve

Full text of DOI:10.1002/chem.200900230

FULL PAPER
DOI: 10.1002/chem.200900230
Multicomponent Supramolecular Systems: Self-Organization in
Coordination-Driven Self-Assembly
Yao-Rong Zheng,[a] Hai-Bo Yang,*[b] Koushik Ghosh,[a] Liang Zhao,[a] and
Peter J. Stang*[a]
Abstract: The self-organization of mul-
ticomponent supramolecular systems
involving a variety of two-dimensional
(2D) polygons and three-dimensional
(3D) cages is presented. Nine self-or-
ganizing systems, SS1–SS9, have been
studied. Each involves the simultane-
ous mixing of organoplatinum accept-
ors and pyridyl donors of varying ge-
ometry and their selective self-assem-
bly into three to four specific 2D (rec-
tangular, triangular, and rhomboid)
and/or 3D (triangular prism and dis-
torted and nondistorted trigonal bipyr-
amidal) supramolecules. The formation
of these discrete structures is character-
ized using NMR spectroscopy and elec-
trospray ionization mass spectrometry
(ESI-MS). In all cases, the self-organi-
zation process is directed by: 1) the
geometric information encoded within
the molecular subunits and 2) a ther-
modynamically driven dynamic self-
correction process. The result is the se-
lective self-assembly of multiple dis-
crete products from
a
randomly
formed complex. The influence of key
experimental variables - temperature
and solvent - on the self-correction
process and the fidelity of the resulting
self-organization systems is also
described.
Keywords: cage compounds · self-
assembly · supramolecular chemis-
try · supramolecular polygons
Introduction
ed fields, such as material science and biochemistry, have
also benefited from merging with supramolecular chemistry.
Examples include the development of supramolecular poly-
mers,[5] DNA nanofabrication,[6] chemical sensing ensem-
bles,[7] drug delivery,[8] and membrane transport agents.[9]
With the continual development of supramolecular chemis-
try over the last three decades one thing has remained large-
ly constant: self-assembly has focused primarily on the for-
mation of a single supramolecular product. This observation
contrasts with biological systems in that complex biological
systems and their corresponding functions are achieved by
the coexistence and collaboration of multiple biological
supramolecular components rather than single discrete
supramolecular species. Examples include DNA replica-
tion,[10] RNA transcription[11] and posttranslational modifica-
tion etc,[12] all of which are accomplished by the collabora-
tion of various enzymes within complex biological systems.
With the aim of obtaining insight into multicomponent bio-
logical systems, it is necessary to explore the controllable
and organized self-assembly of multicomponent supramolec-
ular systems (MSSs).
The implementation of molecular information to direct self-
assembly based on specific noncovalent interactions[1] (e.g.,
hydrogen bonding, metal ligand coordination or electrostatic
forces, etc) has facilitated the rapid development of supra-
molecular chemistry from the pioneering work of Lehn,
Cram, and Pederson[2] to the present detailed investigations
of constructing individual well-defined functionalized inor-
ganic[3] or organic supramolecular structures.[4] Closely relat-
[a] Y.-R. Zheng, K. Ghosh, Dr. L. Zhao, Prof. Dr. P. J. Stang
Department of Chemistry
University of Utah
315 South 1400 East, RM, 2020
Salt Lake City, Utah, 84112 (USA)
Fax : (+1)801-581-8433
E-mail: Stang@chem.utah.edu
[b] Prof. Dr. H.-B. Yang
Shanghai Key Laboratory of Green Chemistry and
Chemical Processes, Department of Chemistry
3663 N. Zhongshan Road
Shanghai, 200062 (China)
Self-organization[13] is a natural phenomenon capable of
spontaneously forming multiple ordered structures from
within a system composed of many individual subunits. By
designing molecular subunits with specific geometric and/or
Fax : (+86)21-62235137
E-mail: hbyang@chem.ecnu.edu.cn
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.200900230.
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electronic properties, self-organization can enable dynamic
self-assembly that extends beyond the formation of a single
supramolecular entity to the simultaneous assembly of mul-
tiple ordered supramolecular structures within one complex
system.[13] Insight into such supramolecular behavior may
open avenues towards the efficient construction of MSSs for
synthetic chemists. Indeed, in the last decade, numerous ef-
forts have been made by pioneers, such as Lehn,[14a] Ray-
mond,[14b] and Isaacs,[13c] to obtain insight into self-organiza-
tion. Following the first example demonstrated by Lehn and
coworkers[14a] wherein multiple different supramolecular hel-
icates were simultaneously self-assembled, synthetic self-or-
ganized systems have been developed based on metal ligand
coordination bonding,[14] hydrogen bonding,[15] solvophobic
effects,[16] and dynamic covalent interactions.[17]
Upon inspection of these pioneering studies, it is found
that the geometric features of molecular subunits play a sig-
nificant role in self-organization. Geometric features enable
the success of the synthetic self-organization and often si-
multaneously dictate the structural features of the assem-
bled supramolecular entities.[14a,b] As a representative exam-
ple of geometrically directed self-organization, Raymond
et al. have demonstrated the simultaneous self-assembly of
three metallo-supramolecular triple helicates that relied
solely on the length of a rigid spacer separating two catecho-
late binging sites.[14b] It is clear that the use of geometric in-
formation within molecular subunits to drive self-organiza-
tion not only enables the assembly of MSSs, but also pro-
vides a means of controlling the structural features of the re-
sulting systems, which is key to manipulating the MSSs. Ex-
ploration of such geometry directing self-organization is
necessary to obtain a greater understanding and better con-
trol of the synthesis of MSSs. To the best of our knowledge,
however, reports focusing on such self-organization are still
relatively few.[14a,b]
In the last few years, the metal ligand coordination-driven
self-assembly of supramolecular polygons and polyhedrons
has been well developed.[18] Since the development of such
self-assembly provides multiple building blocks for achieving
geometry directing coordination-driven self-organization
systems, we have based our entry into MSSs on self-organi-
zation that depends on the geometric features of directional
molecular building blocks.[19] Recently, we have demonstrat-
ed the two-component self-organization of either 2D or 3D
supramolecular structures of varying size or dimensionality
driven by one specific type of geometric information (an-
gle[19a,b] or size[19c]). The high-fidelity self-organization of the
discrete supramolecular species can be achieved, over time,
through a thermodynamically determined self-correction
process by excluding thermodynamically unfavored oligo-
meric species that are derived from the random combination
of different ligands.[19]
the initially formed oligomeric structures.[19] Self-correction
processes in such mixtures require an even greater degree of
selectivity to regulate disordered oligomeric species into dis-
crete supramolecular species. Many different geometric fea-
tures (such as size, angle, and number of binding sites) must
be encoded within the molecular building blocks to conduct
such self-organization. Thus, the development of self-organi-
zation toward higher diversity and complexity involving
multiple 2D and 3D supramolecular structures is a consider-
able challenge.
With the aim of developing MSSs of high structural diver-
sity, we have carried out a detailed study of nine self-organi-
zation systems, SS1–SS9. Each system shows selective self-as-
sembly of three to four 2D and/or 3D supramolecular com-
ponents comprising six different structural motifs (rectangu-
lar,[20] triangular,[21] rhomboid,[22] distorted and nondistorted
triangular prism[23] and triangular bipyramidal[24]). Through
these nine self-organization systems, geometric differences
encoded within the rigid and directional molecular compo-
nents are the major driving force directing the self-organiza-
tion process. Such geometric information both efficiently di-
rects these self-organization processes while excluding the
thermodynamically less favored oligomeric assemblies, and
also reveals the generality of the coordination-driven self-or-
ganization of supramolecular structures. To obtain insight
into the dynamic nature of such complicated supramolecular
self-organization processes, we also explored the effects of
temperature and solvent choice.
Results and Discussion
Self-organization with “molecular clip” 1: Di-platinum(II)
molecular clip 1 has been previously used to self-assemble
individual supramolecular 2D rectangles[20] and 3D triangu-
lar prisms.[23] Self-organization studies involving molecular
clip 1 with pyridyl donors 2–6 may provide an efficient ap-
proach toward the construction of MSSs involving various
2D structures and 3D assemblies.
The self-organization system SS1 was produced by mixing
molecular clip 1 with different sized linear bipyridyl linkers
2 and 3 and a tripyridyl donor 4 in a 7:2:2:2 ratio as shown
in Scheme 1. After heating at 65–708C in an aqueous ace-
tone solution (v/v 1:1) for 24 h, the 2D supramolecular rec-
tangles RS and RL and 3D distorted triangular prism DTPS
were formed as the dominant products. The self-organiza-
tion process was monitored by 31P and 1H multinuclear
NMR spectroscopy as shown in Figure 1 and Figure 2, re-
spectively.
After 1 h of heating at 65–708C, SS1 changed from a sus-
pension to a clear solution. The 31P{1H} NMR spectrum
(Figure 1) of the reaction mixture showed a highly complex
pattern of signals that are representative of disordered oli-
gomeric species as the result of random combinations of
molecular subunits (1, 2, 3, and 4). Similarly, broad peaks
belonging to oligomeric structures were found in the
1H NMR spectrum (Figure 2). Within the ESI mass spec-
As a further step into ordered MSSs of higher complexity,
it is necessary to explore the geometry selective self-organi-
zation of more supramolecular components and higher
structural diversity. Increasing the diversity of molecular
components in the mixtures will amplify the complexity of
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Multicomponent Supramolecular Systems
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Figure 2. 1H NMR spectra ([D6]acetone/D2O 1:1) recorded at 1 h, 6 h,
and 24 h time intervals during the formation of supramolecular rectangles
RS and RL and distorted triangular prism DTPS.
Scheme 1. Graphical representation of self-organization systems SS1–SS4
involving diverse coordination-driven self-assembly: small rectangle (RS),
large rectangle (RL), small distorted triangular prism (DTPS), large dis-
torted triangular prism (DTPL), and nondistorted triangular prism
(NTP).
Figure 3. Full ESI mass spectrum ([D6]acetone/D2O 1:1) recorded after
1 h and 24 h during the self-organization of supramolecular rectangles RS
and RL and distorted triangular prism DTPS.
trum (Figure 3) of the mixture, signals corresponding to
fragments of the randomly formed oligomers can be found
at 1256.6 for [2(1)+2(2)À2NO3]2+
, 899.5 for [2(1)+
2(3)À3NO3]3+, 888.8 for [2(1)+2(4)À3NO3]3+, 858.2 for
[2(1)+(2)+(3)À3NO3]3+
,
1310.0
for
[2(1)+(2)+
(4)À2NO3]2+, and 1372.4 for [2(1)+(3)+(4)À2NO3]2+
,
which further confirm the initially random assembly of these
building blocks shortly after mixing.
After 24 h, however, only three sets of sharp signals (con-
sistent with those previously reported for RS,[20] RL,[20] and
DTPS[23a]) can be observed in the NMR spectra as shown in
Figure 1 and Figure 2, indicating that the initial randomly
Figure 1. 31P{1H} NMR spectra ([D6]acetone/D2O 1:1) recorded at 1 h,
6 h, and 24 h time intervals during the formation of supramolecular rec-
tangles RS and RL and distorted triangular prism DTPS.
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H.-B. Yang, P. J. Stang et al.
formed oligomeric species have been dynamically and selec-
tively converted to specific supramolecular assemblies (RS,
RL, and DTPS) in the equilibrated mixture. The selective
formation of supramolecuar rectangles RS and RL and dis-
torted triangular prism DTPS was further confirmed by ESI
mass spectrometry as shown in Figure 3. The ESI mass
peaks corresponding to the consecutive loss of nitrate
anions from the prism DTPS: m/z=1944.8 [MÀ2NO3]2+ and
m/z=1275.9 [MÀ3NO3]3+ are observed, as are those corre-
sponding to the formation of the different sized rectangles,
Three different self-organization systems SS2-SS4, each in-
volving three of the five species RS, RL, DTPS, DTPL, and
NTP, were prepared by mixing multiple molecular subunits
in an aqueous acetone solution (Scheme 1). Disordered oli-
gomeric species were initially formed in all mixtures as indi-
1
cated by the 31P and the H NMR spectra recorded periodi-
cally for these self-organization systems (see Supporting In-
formation, Figure S5–S7). These disordered mixtures slowly
(24–48 h) converted into the discrete supramolecular struc-
tures via a dynamic self-correction process, as evidenced by
the sharpening of their NMR spectra over a 24–48 h period
of heating at 65–708C. As a result, the assemblies RS, RL,[20]
DTPS, DTPL,[23a] and NTP[23b] were formed as the predomi-
nant species within the self-organization systems SS2–SS4, as
supported by the sharp and identifiable spectroscopic signals
in the 31P{1H} NMR spectra (SS2: 8.32 ppm for RS; 8.83 ppm
for DTPL; 9.81 ppm for DTPS, SS3: 8.32 ppm for RS;
8.48 ppm for RL; 8.65 ppm for NTP, and SS4: 8.32 ppm for
RS; 8.65 ppm for NTP; 9.81 ppm for DTPS; Figure 4). In
both SS3 and SS4 a small peak
RS: m/z=1256.7 [MÀ2NO3]2+ and m/z=816.9 [MÀ3NO3]3+
,
and RL: m/z=1380.3 [MÀ2NO3]2+ and m/z=899.2
[MÀ3NO3]3+, each of which is in agreement with those re-
ported previously.[19c]
The multinuclear NMR and mass spectral results de-
scribed above support the self-organization of RS, RL and
DTPS and also present a typical geometry selective self-or-
ganization process that regulates disordered oligomeric spe-
cies into discrete supramolecular species (Scheme 2).[19]
at 9.01 ppm appears and is be-
lieved to indicate
a
small
amount of disordered byprod-
uct. The 1H NMR spectra
(Figure 5) show intense identifi-
able signals corresponding to
the different discrete supra-
molecular species, each of
which is consistent with that re-
ported previously,[20,23] despite
partial overlapping of some sig-
nals.
Scheme 2. Graphical representation of the self-organization process in SS1 regulating randomly formed and
disordered oligomeric structures into an ordered multicomponent supramolecular system of RS, RL, and DTPS.
The formation of discrete
supramolecular rectangles and
Upon mixing, disordered oligomeric structures can be
formed as major species by random combinations of the mo-
lecular subunits. This is observed in the NMR and ESI-MS
spectra recorded after 1 h. However, the kinetically liable
3D cages in the complex mixtures SS2–SS4 is further charac-
À
nature of the Pt N coordination bond allows a self-correc-
tion process within the mixture and the ultimate product
distribution is determined by the thermodynamic stability of
each species. Disordered oligomeric species of lower stabili-
ty can be dynamically self-corrected to the thermodynami-
cally preferred discrete supramolecular entities,[19] as wit-
nessed by the simplified NMR and ESI-MS spectra recorded
after 24 h. Such thermodynamically driven self-correction
results in the exclusive formation of multiple discrete supra-
molecular entities.
The results of one such study, however, are not able to de-
finitively show whether such geometry directed self-organi-
zation is an exceptional case or a general behavior for the
coordination driven self-assembly of supramolecular poly-
gons and 3D cages. To further understand such geometry di-
recting self-organization processes, the investigation of
mixed self-assemblies incorporating multiple 2D and 3D su-
perstructures RS, RL, DTPS, DTPL, and NTP was carried out
by examining their self-organization behavior.
Figure 4. Equilibrated 31P{1H} NMR spectra ([D6]acetone/D2O 1:1) re-
corded for self-organization systems a) SS2 (RS, DTPS, and DTPL), b) SS3
(RS, RL, and NTP); and c) SS4 (RS, DTPS, and NTP).
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spectra of SS2–SS4: for example, intense peaks for RS: m/z=
1256.7 [MÀ2NO3]2+ and m/z=816.9 [MÀ3NO3]3+, RL:
m/z=1380.3 [MÀ2NO3]2+ and m/z=899.2 [MÀ3NO3]3+
,
DTPS: m/z=1944.8 [MÀ2NO3]2+ and m/z=1275.9
[MÀ3NO3]3+, DTPL: m/z=1474.5 [MÀ3NO3]3+ and m/z=
1090.4 [MÀ4NO3]4+, and NTP: m/z=1354.1 [MÀ3NO3]3+
and m/z=1000.4 [MÀ4NO3]4+. Each of these peaks is con-
sistent with those previously reported.[19b,c] The combined
1
evidence from 31P and H multinuclear NMR spectroscopy
as well as ESI mass spectrometry clearly indicates that high-
fidelity self-organization has been achieved in systems SS2–
SS4.
The geometric information encoded within the size, angle
and number of binding sites of various pyridyl donors is suf-
ficient to direct structurally diverse self-organization involv-
ing different sized 2D supramolecular rectangles (RS and
RL) as well as a variety of 3D triangular prisms (DTPS,
DTPL, and NTP). The successful achievement of self-organi-
zation in systems SS1–SS4 indicates the generality of self-or-
ganization behavior for the self-assembly of these structural
motifs - rectangles and distorted and nondistorted triangular
prisms - which is the first step toward the construction of
highly diverse MSSs by means of self-organization.
Figure 5. Partial 1H NMR spectra ([D6]acetone/D2O 1:1) recorded for
equilibrated self-organization systems a) SS2 (RS, DTPS, and DTPL);
b) SS3 (RS, RL, and NTP); and c) SS4 (RS, DTPS, and NTP).
terized by ESI mass spectrometry (Figure 6). Identifiable
signals for the consecutive loss of nitrate anions from RS,
RL, DTPS, DTPL and NTP can be found in the ESI mass
Self-organization with 608 organoplatinum acceptor 7: To
further demonstrate the generality of geometry selective
self-organization in coordination-driven self-assembly, de-
tailed investigations into supramolecular species assembled
by additional molecular components are necessary. Thus a
608 organoplatinum acceptor,[21] a widely utilized molecular
subunit capable of assembling 2D supramolecular rhom-
boids[25] and triangles[21] as well as 3D triangular bipyra-
mids,[24] has been investigated.
Three different self-organization systems SS5–SS7, each in-
volving three of the five different assemblies TS, TL, RhS,
RhL, and TBP, were prepared as shown in Scheme 3. The
608 organoplatinum acceptor 7 was mixed with complemen-
tary ditopic and tritopic pyridyl donors 2, 3, 5, 8, and 9 in an
aqueous acetone solution (v/v 1:1) and heated at 65–708C.
1
The 31P and H multinuclear NMR spectra of these mixtures
were used to follow these self-organization processes. Signif-
1
icant sharpening over time of both the 31P{1H} and H NMR
spectra was observed for each mixture during continued
heating (24–48 h) (see Figures S8–S10 in the Supporting In-
formation). These results indicate that the previously de-
scribed dynamic self-correction process occurs in these self-
organization systems to regulate the randomly formed disor-
dered oligomeric species into discrete multicomponent as-
semblies. Figure 7 and Figure 8 present the 31P{1H} and the
1H NMR spectra of self-organization systems SS5–SS7 after
full equilibration. As expected, the 31P{1H} NMR spectra for
each of SS5-SS7 (Figure 7a–c) show peaks that are consistent
with those of the individually prepared assemblies (SS5:
14.31 ppm for TS; 14.40 ppm for TBP; 14.43 ppm for RhS,
SS6: 14.31 ppm for TS; 14.38 ppm for RhL; 14.43 ppm for
RhS, and SS7: 14.31 ppm for TS; 14.43 ppm for RhS), though
overlap of signals from TL and RhS of SS7 at 14.41 ppm can
Figure 6. Full ESI mass spectrum ([D6]acetone/D2O 1:1) of equilibrated
self-organizing systems a) SS2 (RS, DTPS, and DTPL); b) SS3 (RS, RL, and
NTP); and c) SS4 (RS, DTPS, and NTP).
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H.-B. Yang, P. J. Stang et al.
Figure 8. Partial 1H NMR spectra ([D6]acetone/D2O 1:1) recorded for
equilibrated self-organizing systems a) SS5 (TS, RhS, and TBP); b) SS6
(TS, RhS, and RhL); and c) SS7 (TS, TL, and RhS).
be seen. In addition, three sets of signals for discrete self-as-
sembled aggregates[19c,21,24,25] in each self-organization
1
system can be clearly identified in each H NMR spectrum
(Figure 8a–c), though some small broad peaks associated
with minor amounts of disordered structures can also be
1
found in the H NMR spectra (SS5: 7.12, 7.82, and 8.12 ppm;
SS6: 7.48 ppm; SS7: 7.48, 8.12, and 8.54 ppm).
Scheme 3. Graphical representation of self-organization systems SS5–SS7
involving diverse coordination-driven self-assembly: small rhomboid
(RhS), large rhomboid (RhL), small triangle (TS), large triangle (TL), and
triangular bipyramid (TBP).
The formation of discrete supramolecular species TS, TL,
RhS, RhL, and TBP in complex mixtures SS5–SS7 is further
supported by ESI mass spectrometry as shown in Figure 9.
Signals for the consecutive loss of nitrate anions from TS,
TL, RhS, RhL, and TBP (TS: m/z=1916.6 [MÀ2NO3]2+ and
m/z=927.06 [MÀ4NO3]4+, TL: m/z=1381.5 [MÀ3NO3]3+
and
m/z=1020.6
[MÀ4NO3]4+
,
RhS:
m/z=1333.4
[MÀ2NO3]2+ and m/z=868.3 [MÀ3NO3]3+, RhL: m/z=
1484.5 [MÀ2NO3]2+ and m/z=969.0 [MÀ3NO3]3+, and
TBP: m/z=1474.5 [MÀ3NO3]3+
and m/z=1090.4
[MÀ4NO3]4+) are observed in the ESI mass spectra and are
consistent with previously reported results.19c,21,24,25 The re-
sults of both multinuclear NMR spectroscopy and ESI mass
spectrometry indicate successful self-organization within sys-
tems SS5–SS7, which incorporate a high degree of structural
diversity (triangles, rhomboids and triangular bipyramids).
Self-organization with both molecular clip 1 and the 608
organoplatinum acceptor 7: Additional investigations ex-
ploring geometry directed self-organization that involves the
combination of two organic donors and two organoplatinum
acceptors have also been performed. Self-organization
system SS8, for example, involves mixing molecular clip 1
and the 608 organoplatinum acceptor 7 with different sized
linear dipyridyl donors 2 and 3 in a 1:1:1:1 ratio in the aque-
ous acetone solution (v/v 1:1). The complex mixture is capa-
ble of simultaneously self-assembling four supramolecular
metallacycles of varying size as shown in Scheme 4. The
Figure 7. Equilibrated 31P{1H} NMR spectra ([D6]acetone/D2O 1:1) re-
corded for self-organizing systems a) SS5 (TS, RhS, and TBP); b) SS6 (TS,
RhS, and RhL); and c) SS7 (TS, TL, and RhS).
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Multicomponent Supramolecular Systems
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1
self-organization process was followed by 31P and H multi-
nuclear NMR spectroscopy (see Figure S11 in the Support-
ing Information). Disordered oligomeric structures were ini-
tially formed as demonstrated by signals at d=7.54, 8.94,
9.11, 14.03, and 15.80 ppm in the 31P{1H} NMR spectra as
1
well as unidentifiable broad peaks in the H NMR spectra
recorded at 6 h and 24 h time intervals. A longer heating
time of 72 h at 65–708C was necessary to accomplish self-or-
1
ganization. The 31P{1H} and the H NMR spectra of the re-
sulting mixture are shown in Figure 10. Four peaks corre-
Figure 9. Full ESI mass spectrum ([D6]acetone/D2O 1:1) of equilibrated
self-organizing systems a) SS5 (TS, RhS, and TBP); b) SS6 (TS, RhS, and
RhL), and c) SS7 (TS, TL, and RhS).
Figure 10. 31P{1H} NMR (a) and Partial 1H NMR (b) spectra
([D6]acetone/D2O 1:1) recorded for equilibrated self-organizing system
SS8 (RS, RL, TS, and TL).
sponding to the different sized supramolecular rectangles
and triangles at 8.32 ppm (RS[20]), 8.48 ppm (RL[20]),
14.32 ppm (TS[21]), and 14.40 ppm (TL[19c]) are seen in the
31P{1H} NMR spectrum (Figure 10a). Likewise, four sets of
signals for these different sized rectangles and triangles can
1
be clearly identified within the H NMR spectrum as shown
in Figure 10b, the chemical shifts of which are consistent
with those previously reported.[19c,20,21] Certain unassignable
signals that are representative of a small amount of disor-
dered byproducts, however, can still be found as small peaks
in the 1H NMR spectrum such as those at d=7.45 and
8.90 ppm. These peaks cannot be eliminated even with
longer heating. ESI mass spectrometry was also used to
characterize the products of SS8. Intense ESI mass peaks
corresponding to the consecutive loss of nitrate anions from
four self-organized supramolecular structures can be ob-
served as shown in Figure S13 in the Supporting Informa-
tion.
The use of two organoplatinum acceptors and two organic
donors in such complex self-organization systems can be ex-
tended to three-dimensions by mixing molecular clip 1 and
the 608 acceptor 7 with ditopic and tritopic pyridyl donors 2
and 5 in a 3:3:3:2 ratio, SS9. This self-organization system is
Scheme 4. Graphical representation of self-organization systems SS8 and
SS9 involving diverse coordination-driven self-assembly: small rectangle
(RS), large rectangle (RL), large distorted triangular prism (DTPL), small
triangle (TS), large triangle (TL), and triangular bipyramid (TBP).
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H.-B. Yang, P. J. Stang et al.
capable of forming 2D supramolecular polygons (rectangle
RS and triangle TS) as well as 3D cages (distorted triangular
prism DTPL and triangular bipyramid TBP) as shown in
during assembly. Furthermore, the use of four molecular
subunits in SS8 and SS9 allows for the simultaneous assembly
of four supramolecular species of high structural diversity,
while only three entities can be formed within SS1–SS7. Such
self-organization provides a more efficient way to assemble
MSSs of high structural diversity.
1
Scheme 4. 31P and H multinuclear NMR spectroscopy were
used to study the self-organization of SS9 as shown in Fig-
ure S12 of the Supporting Information. The mixture re-
mained highly disordered after 6 h of heating, as indicated
by unassignable signals at d=8.83, 13.98, and 15.97 ppm in
the 31P{1H} NMR spectra (Figure S12a). Over time and with
continued heating, these oligomeric peaks decreased as the
peaks of RS, TS, DTPL, and TBP sharpened indicating that
the mixture slowly approached equilibrium. After 96 h of
heating at 65–708C, four different 2D and 3D supramolec-
ular structures (RS, TS, DTPL, and TBP) were generated
from SS9 as supported by 31P and 1H multinuclear NMR
spectroscopy (Figure 11) as well as ESI mass spectrometry
Variables that affect the fidelity of self-organization processes
In addition to differences in geometry, it has been shown
that both temperature and solvent can and do affect self-or-
ganization, and the effects of varying these two parameters
have been investigated in the cases of SS1 and SS6.
Temperature: To investigate the effect of temperature
changes on self-organization processes, the molecular subu-
nits of SS1 were mixed in an aqueous acetone solution (v/v
1:1) and heated at 65–708C for 1 h. As a result, disordered
oligomeric species were formed via the initial random com-
bination of acceptors and donors as implied by the
1
31P{1H} NMR (Figure 12a) and the H NMR (Figure S15a of
Figure 11. 31P{1H} NMR (a) and Partial 1H NMR (b) spectra
([D6]acetone/D2O 1:1) recorded for equilibrated self-organizing system
SS9 (RS, TS, DTPL, and TBP).
Figure 12. 31P{1H} NMR spectra ([D6]acetone/D2O 1:1) recorded for mix-
tures of SS1 (RS, RL, and DTPS) heated at a) 65–708C for 1 h; b) 65–708C
for 24 h; c) 45–508C for 120 h; and d) 25–308C for 20 days.
(Figure S14 in the Supporting Information). In the
31P{1H} NMR spectrum (Figure 11a), peaks at 8.33 ppm
(RS[20]), 8.83 ppm (DTPL[23a]), 14.32 ppm (TS[21]), and
14.39 ppm (TBP[24]) clearly indicate the formation of the
four discrete supramolecular species as the predominant
products of the reaction. Similarly, the 1H NMR spectrum
(Figure 11b) displayed identifiable signals belonging to
RS,[20] TS,[21] DTPL,[23a] and TBP,[24] along with small broad
peaks attributable to disordered structures (7.88 and
9.05 ppm). Data from ESI-MS studies also indicated the for-
mation of the four supramolecular entities (Figure S14).
SS8 and SS9 indicate that self-organization can be ach-
ieved in complex mixtures of two different organoplatinum
acceptors as well as two organic donors. Compared with
self-organization systems SS1–SS7 discussed previously, SS8
and SS9 require longer reaction times (72 h and 96 h) to
reach equilibrium, presumably because of the increased
complexity of the disordered byproducts encountered
the Supporting Information) spectra. This mixture was then
separated into three samples that were kept at 25–308C, 45–
508C, and 65–708C, respectively, until each reached thermo-
1
dynamic equilibrium. 31P and H multinuclear NMR spec-
troscopy were used to monitor the self-organization process
within each mixture. Results from the 31P{1H} NMR spectra
of these three mixtures (Figure 12b–d) as well as the
1H NMR spectra (Figure S15b–d in the Supporting Informa-
tion) indicate that a decrease of temperature causes a signif-
icant decrease in the rate of the self-organization process.
Decreasing the reaction temperature from 65–708C to 45–
508C increased the time required for self-organization from
24 h to 120 h. At even lower temperatures of 25–308C the
self-organization process occurs extremely slowly and did
7210
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Chem. Eur. J. 2009, 15, 7203 – 7214

Multicomponent Supramolecular Systems
FULL PAPER
not reach equilibrium after 20 d. Similar temperature effects
can be found within self-organization system SS6 as indicat-
ed by the multinuclear NMR spectral results shown in Fig-
ures S16 and S17.
assignable signals within the 31P{1H} NMR spectra (Fig-
ure 13b–c) and the appearance of broad signals in the
1H NMR spectra (Figure S18b–c of the Supporting Informa-
tion). Thus, destruction of the ordered supramolecular spe-
cies occurred as a result of the change of solvent for SS1.
However, it was found that the solvent effects on SS1 were
reversible. Upon concentrating the disordered CD2Cl2 and
[D6]acetone/D2O (20:1) mixtures of SS1 to dryness and re-
dissolving in [D6]acetone/D2O (1:1), the self-organized mix-
ture can be achieved again, after 12 h of heating at 65–708C,
as shown by the 31P{1H} (Figure 13d–e) and the 1H (Fig-
ure S18d–e of the Supporting Information) NMR spectra. The
combined evidence indicates that the choice of solvent is
critical to the efficiency of self-organization in the coordina-
tion-driven self-assembly of organoplatinum supramolecules.
Solvent: Self-assembly is also sensitive to changes in solvent,
owing to the different thermodynamic stabilities of species
intermediate and final formed in different media.[20] To test
how solvent affects self-organization, studies of both SS1
and SS6 were carried out in two different solvents: CD2Cl2
and [D6]acetone/D2O (20:1). The self-organized mixtures
were obtained by: 1) initially heating an aqueous acetone
solution (v/v 1:1) for 24 h, then 2) concentrating the solution
to dryness and redissolving in either CD2Cl2 or [D6]acetone/
D2O (20:1), and finally 3) heating each (CD2Cl2: 45–508C;
[D6]acetone/D2O (20:1): 60–658C) until achieving equilibri-
1
um. As indicated by 31P and H multinuclear NMR spectros-
copy (Figure 13, S18, S19, and S20), the change of solvent
shows little effect in SS6, but significantly effects the self-or-
ganization system SS1.
Conclusions
In summary, the thermodynamically driven self-organization
of nine different complex mixtures (SS1–SS9) has been clear-
ly demonstrated. Each mixture is capable of spontaneously
and selectively producing multiple discrete supramolecular
structures at the exclusion of less stable disordered assem-
blies. The selective formation of discrete self-organized
products is supported by multinuclear NMR spectroscopy
and ESI mass spectrometry. Various supramolecular species,
from the self-assembly of 2D supramolecular polygons to
3D polyhedra, can be self-organized within complex mix-
tures containing a variety of complementary molecular sub-
units. Self-organization proceeds via a thermodynamically
determined self-correction process that is largely dependent
on the geometric information pre-coded within the subunits.
Additionally, the experimental variables of temperature and
solvent have been investigated and shown capable of affect-
ing these self-organization systems. As expected, tempera-
ture changes have a dramatic effect on the rate of the self-
organization process. Different solvents present a significant,
yet reversible, change in the fidelity of self-organization.
More importantly, the successful self-organization in sys-
tems SS1–SS9, including ten different 2D and 3D supra-
molecular structures (RS, RL, DTPS, DTPL, NTP, TS, TL,
RhS, RhL, and TBP) and six different structural motifs (rec-
tangle, triangle, rhomboid, normal, and distorted triangular
prism, and triangular bipyramid), reveals the generality of
geometry directed self-organization behavior in coordina-
tion-driven self-assembly of supramolecular polygons and
cages. The results also represent a promising approach
toward the build-up of structurally diverse multicomponent
supramolecular systems (MSSs). The implications of this re-
search go beyond the comprehensive study of geometry se-
lective self-organization in coordination driven self-assembly
as many recent reports have been focused on the synthesis
and self-assembly of functionalized supramolecules.[26] Pro-
vided that high-fidelity self-organization can be extended to
these new functionalized systems, the current research can
be extended to the development of muti-funcitonalized
Figure 13. 31P{1H} NMR spectra of SS1 in various solvents:
a) [D6]acetone/D2O (1:1), b) CD2Cl2, c) [D6]acetone/D2O (20:1),
d) [D6]acetone/D2O (1:1) after removal of CD2Cl2, and e) [D6]acetone/
D2O (1:1) after removal of [D6]acetone/D2O (20:1).
Mixtures of SS6 in either CD2Cl2 or [D6]acetone/D2O
(20:1) were shown capable of self-organization after 36 h of
heating as indicated by identifiable signals corresponding to
the discrete supramolecular species in the 31P{1H} and the
1H NMR spectra (Figure S19 and S20 of the Supporting In-
formation). However, in the case of SS1, the initially organ-
ized supramolecular mixtures of RS, RL, and DTPS that were
transferred to CD2Cl2 and [D6]acetone/D2O (20:1) solutions
were significantly disordered after 36 h of heating. The three
original intense peaks with were replaced by multiple un-
Chem. Eur. J. 2009, 15, 7203 – 7214
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
7211

H.-B. Yang, P. J. Stang et al.
PCH2CH3), 0.84 ppm (m, 72H; PCH2CH3); DTPS: d=9.14 (d, 6H; 3J=
6.3 Hz, HaÀPy), 8.98 (m, 9H; Ha’ÀPy,9), 8.36 (s, 3H; H10), 8.25 (d, 6H; 3J=
4.2 Hz, HbÀPy), 7.72 (m, 12H; Hb’ÀPy, H4, 5), 7.68 (d, 6H; 3J=9.9 Hz, H2,7),
7.14 (m, 6H; H3,6), 1.40 (m, 72H; PCH2CH3), 0.82 ppm (m, 108H;
PCH2CH3); DTPL: d=9.32 (s, 3H; H9), 9.01 (d, 6H; 3J=5.1 Hz, HaÀPy),
8.91 (d, 6H; 3J=4.8 Hz, Ha’ÀPy), 8.36 (s, 3H; H10), 8.00 (d, 6H; 3J=
6.0 Hz, HbÀPy), 7.95 (d, 6H; 3J=6.0 Hz, HbÀPy), 7.73 (m, 12H; H4,5,2,7),
7.57 (d, 12H; 3J=8.4 Hz, H3,5Àphenylene), 7.17 (d, 12H; 3J=8.1 Hz,
H2,6Àphenylene), 7.14 (m, 6H; H3,6), 1.40 (m, 72H; PCH2CH3), 0.82 ppm (m,
108H; PCH2CH3); 31P{1H} NMR ([D6]acetone/D2O: 1/1, 121.4 MHz) for
RS: d=8.32 ppm (195Pt satellites, 1JPtÀP =2636 Hz); DTPS: d=9.81 ppm
MSSs. The spontaneous self-assembly and self-organization
of multiple, discrete, functionalized supramolecules could
lead to integrated systems wherein many functional mole-
cules are able to collaborate to achieve functions in a
manner akin to natural biological systems. Thus, we envision
that detailed studies of the self-organization of MSSs can
pave the way toward the construction of complex, functional
systems and have implications in the related processes that
govern the assembly of more complex biological structures.
(
195Pt satellites, 1JPtÀP =2649 Hz); DTPL: d=8.83 ppm (195Pt satellites,
1JPtÀP =2655 Hz); MS (ESI) for RS (C96H152N8O12P8Pt4): m/z: 1256.7
[MÀ2NO3]2+
,
816.9 [MÀ3NO3]3+
; DTPS (C146H230N12O20P12Pt6): m/z:
Experimental Section
1944.8 [MÀ2NO3]2+, 1275.9 [MÀ3NO3]3+; DTPL (C196H258N12O18P12Pt6):
m/z: 1474.5 [MÀ3NO3]3+, 1090.4 [MÀ4NO3]4+
Self-organization system SS3 (RS, RL, and NTP): Molecular “Clip” 1
(16.09 mg, 0.01383 mmol), 4,4’-dipyridyl 2 (0.60 mg, 0.0038 mmol), 1,4-
.
Methods and materials: Molecular building blocks 1,[20] 3,[19c] 4,[23a] 5,[23a]
6,[23b] and 7[21] were prepared according to literature procedures. Deuter-
ated solvents were purchased from Cambridge Isotope Laboratory (And-
over, MA). NMR spectra were recorded by using a Varian Unity 300
spectrometer and 500 spectrometer. The 1H NMR chemical shifts are re-
ported relative to residual solvent signals, and 31P NMR resonances are
referenced to an external unlocked sample of 85% H3PO4 (d=0.0). Mass
spectra for SS1–SS9 were recorded by using a Micromass Quattro II
triple-quadrupole mass spectrometer using electrospray ionization with a
MassLynx operating system.
bis(4-pyridylethynyl)benzene
3 (1.16 mg, 0.00414 mmol) and tritopic
tecton 6 (1.49 mg, 0.00391 mmol) were added to 2.0 mL of mixed solvent.
After 48 h heating, RS, RL and NTP were formed predominantly.
1H NMR ([D6]acetone/D2O: 1/1, 300 MHz) for RS: d=9.53 (s, 2H; H9),
9.21 (d, 3J=5.8 Hz, 4H; HaÀPy), 9.18 (d, 3J=5.4 Hz, 2H; Ha’ÀPy), 8.71 (d,
3
3J=5.4 Hz, 4H; HbÀPy), 8.53 (d, J=5.4 Hz, 4H; Hb’ÀPy), 8.37 (s, 2H; H10),
7.71 (d, 3J=10.5 Hz, 4H; H4,5), 7.62 (m, 4H; H2,7), 7.14 (t, 3J=7.2 Hz,
4H; H3,6), 1.45 (m, 48H; PCH2CH3), 0.84 ppm (m, 72H; PCH2CH3); RL:
General procedure for self-organization: Appropriate organoplatinum
acceptors and pyridyl donors were placed in a 2Dram vial, followed by
the addition of the mixed solvent [D6]acetone/D2O (v/v 1:1), which was
then sealed with Teflon tape and immersed in an oil bath at 65–708C.
The clear solution was periodically transferred to an NMR tube for anal-
ysis. After three or four sets of signals corresponding to discrete supra-
molecular structures were clearly presented in the NMR spectra with no
further changes, the reaction mixture was then characterized by using
ESI-MS.
3
d=9.45 (s, 2H; H9), 9.02 (m, 4H; HaÀPy), 8.94 (d, 4H; J=5.4 Hz, Ha’ÀPy),
8.36 (s, 2H; H10), 8.03 (m, 8H; HbÀPy), 7.74 (s, 8H; Hphenylene), 7.71 (d,
4H; 3J=10.5 Hz, H4, 5), 7.64 (m, 4H; H2,7), 7.14 (t, 3J=7.2 Hz, 4H; H3,6),
1.45 (m, 48H; PCH2CH3), 0.84 ppm (m, 72H; PCH2CH3); NTP: d=9.41
3
(s, 3H; H9), 9.02 (m, 6H; HaÀPy), 8.90 (d, 6H; J=5.4 Hz, Ha’ÀPy), 8.36 (s,
3H; H10), 7.92 (m, 12H; HbÀPy), 7.69 (d, 6H; 3J=9.9 Hz, H2,7), 7.85 (s,
6H; HBenzene), 7.62 (d, 6H; 3J=9.9 Hz, H2,7), 7.15 (m, 6H; H3,6), 1.40 (m,
72H; PCH2CH3), 0.82 ppm (m, 108H; PCH2CH3); 31P{1H} NMR
([D6]acetone/D2O: 1/1, 121.4 MHz) for RS: d=8.33 ppm (195Pt satellites,
Self-organization system SS1 (RS, RL, and DTPS): Molecular “Clip” 1
(10.56 mg, 0.00908 mmol), 4,4’-dipyridyl 2 (0.40 mg, 0.0026 mmol), 1,4-
1
1JPtÀP =2648 Hz); RL: d=8.48 (195Pt satellites, JPtÀP =2648 Hz); NTP: d=
8.65 ppm
(
195Pt satellites, 1JPtÀP =2648 Hz); MS (ESI) for RS
bis(4-pyridylethynyl)benzene
3 (0.71 mg, 0.0025 mmol) and tritopic
(C96H152N8O12P8Pt4): m/z: 1256.7 [MÀ2NO3]2+, 816.9 [MÀ3NO3]3+; RL
tecton 4 (0.70 mg, 0.0026 mmol) were added to 1.1 mL of mixed solvent.
After 24 h heating, RS, RL and DTPS were formed predominantly.
1H NMR ([D6]acetone/D2O: 1/1, 300 MHz) for RS: d=9.53 (s, 2H; H9),
9.21 (d, 3J=5.8 Hz, 4H; HaÀPy), 9.18 (d, 3J=5.4 Hz, 2H; Ha’ÀPy), 8.71 (d,
(C116H160N8O12P8Pt4): m/z: 1380.3 [MÀ2NO3]2+
,
899.2 [MÀ3NO3]3+
;
NTP (C168H234N12O18P12Pt6): m/z: 1354.1 [MÀ3NO3]3+
,
1000.4
[MÀ4NO3]4+
.
Self-organization system SS4 (RS, DTPS, and NTP): Molecular “Clip” 1
(13.43 mg, 0.01155 mmol), 4,4’-dipyridyl 2 (0.49 mg, 0.0031 mmol), tritop-
ic tectons 4 (0.73 mg, 0.0028 mmol) and 6 (1.08 mg, 0.00283 mmol) were
added to 2.0 mL of mixed solvent. After 48 h heating, RS, DTPS and
NTP were formed predominantly. 1H NMR ([D6]acetone/D2O: 1/1,
300 MHz) for RS: d=9.53 (s, 2H; H9), 9.21 (d, 3J=5.8 Hz, 4H; HaÀPy),
9.18 (d, 3J=5.4 Hz, 2H; Ha’ÀPy), 8.71 (d, 3J=5.4 Hz, 4H; HbÀPy), 8.53 (d,
3
3J=5.4 Hz, 4H; HbÀPy), 8.53 (d, J=5.4 Hz, 4H; Hb’ÀPy), 8.37 (s, 2H; H10),
7.71 (d, 3J=10.5 Hz, 4H; H4,5), 7.62 (m, 4H; H2,7), 7.14 (t, 3J=7.2 Hz,
4H; H3,6), 1.45 (m, 48H; PCH2CH3), 0.84 ppm (m, 72H; PCH2CH3); RL:
d=9.45 (s, 2H; H9), 9.03 (d, 4H; 3J=5.1 Hz, HaÀPy), 8.95 (d, 4H; 3J=
5.4 Hz, Ha’ÀPy), 8.36 (s, 2H; H10), 8.03 (m, 8H; HbÀPy), 7.74 (s, 8H;
3
3
Hphenylene), 7.71 (d, 4H; J=10.5 Hz, H4, 5), 7.64 (m, 4H; H2,7), 7.14 (t, J=
7.2 Hz, 4H; H3,6), 1.45 (m, 48H; PCH2CH3), 0.84 ppm (m, 72H;
3
3J=5.4 Hz, 4H; Hb’ÀPy), 8.37 (s, 2H; H10), 7.71 (d, J=10.5 Hz, 4H; H4,5),
PCH2CH3); DTPS: d=9.14 (d, 6H; 3J=6.3 Hz, HaÀPy), 8.98 (m, 9H;
H
2,7), 7.14 (t, 3J=7.2 Hz, 4H; H3,6), 1.45 (m, 48H;
3
7.62 (m, 4H;
H
H
a’ÀPy,9), 8.36 (s, 3H; H10), 8.25 (d, 6H; J=4.2 Hz, HbÀPy), 7.72 (m, 12H;
b’ÀPy, H4, 5), 7.68 (d, 6H; 3J=9.9 Hz, H2,7), 7.14 (m, 6H; H3,6), 1.40 (m,
PCH2CH3), 0.84 ppm (m, 72H; PCH2CH3); DTPS: d=9.14 (d, 6H; 3J=
6.3 Hz, HaÀPy), 8.98 (m, 9H; Ha’ÀPy,9), 8.36 (s, 3H; H10), 8.25 (d, 6H; 3J=
4.2 Hz, HbÀPy), 7.72 (m, 12H; Hb’ÀPy, H4, 5), 7.68 (d, 6H; 3J=9.9 Hz, H2,7),
7.14 (m, 6H; H3,6), 1.40 (m, 72H; PCH2CH3), 0.82 ppm (m, 108H;
PCH2CH3); NTP: d=9.41 (s, 3H; H9), 9.02 (m, 6H; HaÀPy), 8.90 (d, 6H;
3J=5.4 Hz, Ha’ÀPy), 8.36 (s, 3H; H10), 7.92 (m, 12H; HbÀPy), 7.69 (d, 6H;
72H; PCH2CH3), 0.82 ppm (m, 108H; PCH2CH3); 31P{1H} NMR
([D6]acetone/D2O: 1/1, 121.4 MHz) for RS: d=8.32 ppm (195Pt satellites,
1JPtÀP =2640 Hz); RL: d=8.48 ppm
(
195Pt satellites, 1JPtÀP =2640 Hz);
DTPS: d=9.81 ppm (195Pt satellites, 1JPtÀP =2651 Hz); MS (ESI) for RS
(C96H152N8O12P8Pt4): m/z: 1256.7 [MÀ2NO3]2+, 816.9 [MÀ3NO3]3+; RL
3
3J=9.9 Hz, H2,7), 7.85 (s, 6H; HBenzene), 7.62 (d, 6H; J=9.9 Hz, H2,7), 7.15
(C116H160N8O12P8Pt4): m/z: 1380.3 [MÀ2NO3]2+
,
899.2 [MÀ3NO3]3+
;
DTPS (C146H230N12O20P12Pt6): m/z: 1944.8 [MÀ2NO3]2+
,
1275.9
(m, 6H;
H3,6), 1.40 (m, 72H; PCH2CH3), 0.82 ppm (m, 108H;
PCH2CH3); 31P{1H} NMR ([D6]acetone/D2O: 1/1, 121.4 MHz) for RS: d=
[MÀ3NO3]3+
.
8.33 ppm (195Pt satellites, 1JPtÀP =2651 Hz); DTPS: d=9.81 ppm (195Pt sat-
Self-organization system SS2 (RS, DTPS, and DTPL): Molecular “Clip” 1
(11.98 mg, 0.0103 mmol), 4,4’-dipyridyl 2 (0.43 mg, 0.0028 mmol), tritopic
tectons 4 (0.68 mg, 0.0026 mmol) and 5 (1.35 mg, 0.0024 mmol) were
added to 1.1 mL of mixed solvent. After 24 h heating, RS, DTPS and
DTPL were formed predominantly. 1H NMR ([D6]acetone/D2O: 1/1,
300 MHz) for RS: d=9.53 (s, 2H; H9), 9.21 (d, 3J=5.8 Hz, 4H; HaÀPy),
9.18 (d, 3J=5.4 Hz, 2H; Ha’ÀPy), 8.71 (d, 3J=5.4 Hz, 4H; HbÀPy), 8.53 (d,
ellites, 1JPtÀP =2654 Hz); NTP: d=8.65 ppm
(
195Pt satellites, JPtÀP
=
1
2651 Hz); MS (ESI) for RS (C96H152N8O12P8Pt4): m/z: 1256.7
[MÀ2NO3]2+
,
816.9 [MÀ3NO3]3+
; DTPS (C146H230N12O20P12Pt6): m/z:
1944.8 [MÀ2NO3]2+, 1275.9 [MÀ3NO3]3+; NTP (C168H234N12O18P12Pt6):
m/z: 1354.1 [MÀ3NO3]3+, 1000.4 [MÀ4NO3]4+
Self-organization system SS5 (TS, RhS, and TBP): 608 organoplatinum ac-
.
3
3J=5.4 Hz, 4H; Hb’ÀPy), 8.37 (s, 2H; H10), 7.71 (d, J=10.5 Hz, 4H; H4,5),
ceptor
7
(13.01 mg, 0.01119 mmol), 4,4’-dipyridyl
2
(0.51 mg,
7.62 (m, 4H; H2,7), 7.14 (t, 3J=7.2 Hz, 4H; H3,6), 1.45 (m, 48H;
0.0033 mmol), 2,6-dipyridyl pyridine 8 (0.76 mg, 0.0033 mmol) and tritop-
7212
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Chem. Eur. J. 2009, 15, 7203 – 7214

Multicomponent Supramolecular Systems
FULL PAPER
3
ic tecton 5 (1.75 mg, 0.00312 mmol) were added to 1.2 mL of mixed sol-
vent. After 24 h heating, TS, RhS and TBP were formed predominantly.
1H NMR ([D6]acetone/D2O: 1/1, 300 MHz) for TS: d=9.16 (d, 3J=
5.7 Hz, 6H; HaÀPy), 9.09 (d, 3J=5.7 Hz, 6H; Ha’ÀPy), 8.65 (s, 6H; H4,5),
8.35 (m, 12H; HbÀPy), 7.54 (m, 18H; H1,2,7,8,9,10), 1.33 (m, 72H; PCH2CH3),
8.37 (s, 2H; H10), 7.71 (d, J=10.5 Hz, 4H; H4,5), 7.62 (m, 4H; H2,7), 7.14
(t, 3J=7.2 Hz, 4H; H3,6), 1.45 (m, 48H; PCH2CH3), 0.84 ppm (m, 72H;
PCH2CH3); RL: d=9.45 (s, 2H; H9), 9.02 (m, 4H; HaÀPy), 8.94 (d, 4H;
3J=5.4 Hz, Ha’ÀPy), 8.36 (s, 2H; H10), 8.03 (m, 8H; HbÀPy), 7.74 (s, 8H;
3
3
H
phenylene), 7.71 (d, 4H; J=10.5 Hz, H4, 5), 7.64 (m, 4H; H2,7), 7.14 (t, J=
3
7.2 Hz, 4H; H3,6), 1.45 (m, 48H; PCH2CH3), 0.84 ppm (m, 72H;
PCH2CH3); TS: d=9.16 (d, 3J=5.7 Hz, 6H; HaÀPy), 9.06 (m, 6H; Ha’ÀPy),
8.65 (s, 6H; H4,5), 8.35 (m, 12H; HbÀPy), 7.54 (m, 18H; H1,2,7,8,9,10), 1.33
(m, 72H; PCH2CH3), 1.05 ppm (m, 108H; PCH2CH3); TL: d=8.90 (m,
12H; HaÀPy), 8.62 (s, 6H; H4,5), 7.84 (d, 12H; 3J=6.6 Hz, HbÀPy), 7.73 (s,
12H; Hphenylene), 7.54 (m, 18H; H1,2,7,8,9,10), 1.30 (m, 72H; PCH2CH3),
1.07 ppm (m, 108H; PCH2CH3); 31P{1H} NMR ([D6]acetone/D2O: 1/1,
121.4 MHz) for RS: d=8.33 ppm (195Pt satellites, 1JPtÀP =2639 Hz); RL:
1.05 ppm (m, 108H; PCH2CH3); RhS: d=9.09 (d, 4H; J=5.7 Hz, HaÀPy),
8.87 (m, 4H; Ha’ÀPy), 8.62 (s, 4H; H4,5), 8.41 (m, 12H; HbÀPy, 3,5ÀPy), 8.25
(m, 2H; H4ÀPy), 7.54 (m, 12H; H1,2,7,8,9,10), 1.33 (m, 48H; PCH2CH3),
1.05 ppm (m, 72H; PCH2CH3); TBP: d=8.91 (m, 12H; HaÀPy), 8.61 (s,
6H; H4,5), 7.78 (m, 12H; HbÀPy), 7.54 (m, 30H; H1,2,7,8,9,10, aÀPhenylene), 7.15
(d, 12H; 3J=8.7 Hz, H1,2,7,8,9,10, bÀPhenylene), 1.33 (m, 72H; PCH2CH3),
1.05 ppm (m, 108H; PCH2CH3); 31P{1H} NMR ([D6]acetone/D2O: 1/1,
121.4 MHz) for TS: d=14.31 ppm (195Pt satellites, 1JPtÀP =2695 Hz); RhS:
d=14.42 ppm (195Pt satellites, 1JPtÀP =2695 Hz); TBP: d=14.38 (195Pt sat-
ellites, 1JPtÀP =2695 Hz); MS (ESI) for TS (C144H228N12O18P12Pt6): m/z:
1916.6 [MÀ2NO3]2+, 927.06 [MÀ4NO3]4+; RhS (C106H158N10O12P8Pt4): m/z:
1333.4 [MÀ2NO3]2+, 868.3 [MÀ3NO3]3+; TBP (C146H230N12O20P12Pt6):
d=8.48 ppm (195Pt satellites, 1JPtÀP =2639 Hz); TS: d=14.32 ppm (195Pt
satellites, 1JPtÀP =2673 Hz); TL: d=14.40 ppm
(
195Pt satellites, JPtÀP
=
1
2673 Hz); MS (ESI) for RS (C96H152N8O12P8Pt4): m/z: 1256.7
[MÀ2NO3]2+, 816.9 [MÀ3NO3]3+; RL (C116H160N8O12P8Pt4): m/z: 1380.3
[MÀ2NO3]2+, 899.2 [MÀ3NO3]3+; TS (C144H228N12O18P12Pt6): m/z: 1916.6
m/z: 1474.5 [MÀ3NO3]3+, 1090.4 [MÀ4NO3]4+
.
[MÀ2NO3]2+
,
927.06 [MÀ4NO3]4+
;
TL (C174H240N12O18P12Pt6): m/z:
.
Self-organization system SS6 (TS, RhS, and RhL): 608 organoplatinum ac-
1381.5 [MÀ3NO3]3+, 1020.6 [MÀ4NO3]4+
ceptor
7
(9.96 mg, 0.00856 mmol), 4,4’-dipyridyl
2
(0.45 mg,
Self-organization system SS9 (RS, DTPL, TS, and TBP): Molecular “Clip”
0.0029 mmol), 2,6-dipyridyl pyridine 8 (0.67 mg, 0.0029 mmol) and bis(4-
(pyridin-4-ylethynyl)phenyl) methanone 9 (1.08 mg, 0.00281 mmol) were
added to 1.4 mL of mixed solvent. After 24 h heating, TS, RhS and RhL
were formed predominantly. 1H NMR ([D6]acetone/D2O: 1/1, 300 MHz)
for TS: d=9.16 (d, 3J=5.7 Hz, 6H; HaÀPy), 9.06 (m, 6H; Ha’ÀPy), 8.65 (s,
6H; H4,5), 8.35 (m, 12H; HbÀPy), 7.54 (m, 18H; H1,2,7,8,9,10), 1.33 (m, 72H;
PCH2CH3), 1.05 ppm (m, 108H; PCH2CH3); RhS: d=9.06 (m, 4H;
1
(7.52 mg, 0.00647 mmol), 608 organoplatinum acceptor 7 (7.50 mg,
0.00645 mmol), 4,4’-dipyridyl 2 (1.00 mg, 0.00640 mmol) and tritopic tec-
tons 5 (2.43 mg, 0.00433 mmol) were added to 1.2 mL of mixed solvent.
After 96 h heating, RS, DTPL, TS, and TBP were formed predominantly.
1H NMR ([D6]acetone/D2O: 1/1, 500 MHz) for RS: d=9.53 (s, 2H; H9),
9.21 (d, 3J=5.8 Hz, 4H; HaÀPy), 9.18 (d, 3J=5.4 Hz, 2H; Ha’ÀPy), 8.71 (d,
3J=5.4 Hz, 4H; HbÀPy), 8.53 (d, J=5.4 Hz, 4H; Hb’ÀPy), 8.37 (s, 2H; H10),
3
H
aÀPy), 8.87 (m, 4H; Ha’ÀPy), 8.62 (s, 4H; H4,5), 8.41 (m, 12H; HbÀPy,
7.71 (d, 3J=10.5 Hz, 4H; H4,5), 7.62 (m, 4H; H2,7), 7.14 (t, 3J=7.2 Hz,
4H; H3,6), 1.45 (m, 48H; PCH2CH3), 0.84 ppm (m, 72H; PCH2CH3);
DTPL: d=9.32 (s, 3H; H9), 9.01 (d, 6H; 3J=5.1 Hz, HaÀPy), 8.91 (d, 6H;
3,5ÀPy), 8.25 (m, 2H; H4ÀPy), 7.54 (m, 12H; H1,2,7,8,9,10), 1.33 (m, 48H;
PCH2CH3), 1.05 ppm (m, 72H; PCH2CH3); RhL: d=8.92 (d, 8H; 3J=
6.0 Hz, HaÀPy), 8.58 (s, 4H; H4,5),7.84 (m, 8H; HbÀPy), 7.81 (s, 8H;
HPhenylene), 7.54 (m, 16H; H1,2,7,8,9,10), 1.33 (m, 48H; PCH2CH3), 1.05 ppm
(m, 72H; PCH2CH3); 31P{1H} NMR ([D6]acetone/D2O: 1/1, 121.4 MHz)
3J=4.8 Hz, Ha’ÀPy), 8.36 (s, 3H; H10), 8.00 (d, 6H; J=6.0 Hz, HbÀPy), 7.95
3
(d, 6H; 3J=6.0 Hz, HbÀPy), 7.73 (m, 12H; H4,5,2,7), 7.57 (d, 12H; 3J=
8.4 Hz, H3,5Àphenylene), 7.17 (d, 12H; 3J=8.1 Hz, H2,6Àphenylene), 7.14 (m, 6H;
H3,6), 1.40 (m, 72H; PCH2CH3), 0.82 ppm (m, 108H; PCH2CH3); TS: d=
9.16 (d, 3J=5.7 Hz, 6H; HaÀPy), 9.06 (m, 6H; Ha’ÀPy), 8.65 (s, 6H; H4,5),
8.35 (m, 12H; HbÀPy), 7.54 (m, 18H; H1,2,7,8,9,10), 1.33 (m, 72H; PCH2CH3),
1.05 ppm (m, 108H; PCH2CH3); TBP: d=8.91 (m, 12H; HaÀPy), 8.61 (s,
6H; H4,5), 7.78 (m, 12H; HbÀPy), 7.54 (m, 30H; H1,2,7,8,9,10, aÀPhenylene), 7.15
(d, 12H; 3J=8.7 Hz, H1,2,7,8,9,10, bÀPhenylene), 1.33 (m, 72H; PCH2CH3),
1.05 ppm (m, 108H; PCH2CH3); 31P{1H} NMR ([D6]acetone/D2O: 1/1,
for TS: d=14.32 ppm
(
195Pt satellites, 1JPtÀP =2690 Hz); RhS: d=
1
14.43 ppm (195Pt satellites, JPtÀP =2690 Hz); RhL: d=14.39 ppm (195Pt sat-
ellites, 1JPtÀP =2690 Hz); MS (ESI) for TS (C144H228N12O18P12Pt6): m/z:
1916.6 [MÀ2NO3]2+
,
927.06 [MÀ4NO3]4+
; RhS (C106H158N10O12P8Pt4):
m/z: 1333.4 [MÀ2NO3]2+, 868.3 [MÀ3NO3]3+; RhL (C130H168N8O14P8Pt4):
m/z: 1484.5 [MÀ2NO3]2+, 969.0 [MÀ3NO3]3+
.
Self-organization system SS7 (TS, TL, and RhS): 608 organoplatinum ac-
121.4 MHz) for RS: d=8.33 ppm (195Pt satellites, JPtÀP =2638 Hz); DTPL:
1
ceptor
0.0027 mmol), 1,4-bis(4-pyridylethynyl)benzene 3 (0.71 mg, 0.0025 mmol)
and 2,6-dipyridyl pyridine (0.63 mg, 0.0027 mmol) were added to
7
(9.21 mg, 0.00792 mmol), 4,4’-dipyridyl
2
(0.42 mg,
d=8.83 ppm (195Pt satellites, 1JPtÀP =2637 Hz); TS: d=14.32 ppm (195Pt
satellites, 1JPtÀP =2667 Hz); TBP: d=14.39 ppm (195Pt satellites, JPtÀP
=
1
8
1.2 mL of mixed solvent. After 48 h heating, TS, TL, and RhS were
2667 Hz); MS (ESI) for RS (C96H152N8O12P8Pt4): m/z: 1256.7
formed predominantly. 1H NMR ([D6]acetone/D2O: 1/1, 300 MHz) for
[MÀ2NO3]2+
,
816.9 [MÀ3NO3]3+
; DTPL (C196H258N12O18P12Pt6): m/z:
3
1474.5 [MÀ3NO3]3+, 1090.4 [MÀ4NO3]4+; TS (C144H228N12O18P12Pt6): m/z:
1916.6 [MÀ2NO3]2+, 927.06 [MÀ4NO3]4+; TBP (C146H230N12O20P12Pt6):
TS: d=9.16 (d, J=5.7 Hz, 6H; HaÀPy), 9.06 (m, 6H; Ha’ÀPy), 8.65 (s, 6H;
H
4,5), 8.35 (m, 12H; HbÀPy), 7.54 (m, 18H; H1,2,7,8,9,10), 1.33 (m, 72H;
m/z: 1474.5 [MÀ3NO3]3+, 1090.4 [MÀ4NO3]4+
.
PCH2CH3), 1.05 ppm (m, 108H; PCH2CH3); TL: d=8.90 (m, 12H;
H
H
aÀPy), 8.62 (s, 6H; H4,5), 7.84 (d, 12H; 3J=6.6 Hz, HbÀPy), 7.73 (s, 12H;
phenylene), 7.54 (m, 18H; H1,2,7,8,9,10), 1.30 (m, 72H; PCH2CH3), 1.07 ppm
(m, 108H; PCH2CH3); RhS: d=9.06 (m, 4H; HaÀPy), 8.87 (m, 4H;
a’ÀPy), 8.62 (s, 4H; H4,5), 8.41 (m, 12H; HbÀPy, 3,5ÀPy), 8.25 (m, 2H; H4ÀPy),
H
7.54 (m, 12H; H1,2,7,8,9,10), 1.33 (m, 48H; PCH2CH3), 1.05 ppm (m, 72H;
PCH2CH3); 31P{1H} NMR ([D6]acetone/D2O: 1/1, 121.4 MHz) for TS: d=
Acknowledgements
14.32 ppm (195Pt satellites, 1JPtÀP =2687 Hz); TL: d=14.42 ppm (195Pt satel-
1
lites, 1JPtÀP =2687 Hz); RhS: d=14.42 ppm
(
195Pt satellites, JPtÀP
=
P.J.S. thanks the NIH (Grant GM-057052) for financial support. We
thank Dr. Brian H. Northrop for helpful discussions and assistance with
revisions.
2687 Hz); MS (ESI) for TS (C144H228N12O18P12Pt6): m/z: 1916.6
[MÀ2NO3]2+
,
927.06 [MÀ4NO3]4+
; TL (C174H240N12O18P12Pt6): m/z:
1381.5 [MÀ3NO3]3+
,
1020.6 [MÀ4NO3]4+
; RhS (C106H158N10O12P8Pt4):
.
m/z: 1333.4 [MÀ2NO3]2+, 868.3 [MÀ3NO3]3+
Self-organization system SS8 (RS, RL, TS, and TL): Molecular “Clip” 1
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Chem. Eur. J. 2009, 15, 7203 – 7214
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
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Received: January 27, 2009
Published online: June 19, 2009
7214
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