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Perturbation of ligand or complex has been widely used across various scientific fields and disciplines, under the

elements of molecular recognition, to sense and signal specific substrates, including cations, as already observed,
anions [148] molecules or larger biological structures, such as DNA [149]. Application of this method has been largely
exploited for abiotic systems, while the development of the related area of luminescence imaging for biomedical
applications has emerged more recently on account of its noninvasive character [150–154]. Accordingly, luminescent
sensors are now available for the detection of Na+ in blood [155,156], of free Li+ in blood and serum [157], for Ca2+ in
damage bones [156], of Zn2+ in various biological samples [152,158,159], to say a few.
Several lanthanide ions are luminescent, emitting either in the visible or in the NIR regions. From this point of view, they
are ideal for biological applications. Nevertheless, their absorption bands are commonly small, so that it is difficult to
populate their excited states. This inconvenience can be overcome by coupling these cations with ligands bearing
chromophore possessing the appropriate excited-state energy to sensitize the metal. By using this strategy (antenna
effect), many lanthanide-based emitters have been generated for sensing applications [160–165]. The use of NIR
emitting probes is of particular interest for applications in biological systems, since these are transparent to the NIR
light, and then the only luminescence emerging from a biological sample containing such NIR emitting sensor would be
that of the sensor itself.
The dynamics and reversibility of supramolecular interactions are particularly suitable for applications in molecular
computation. These interactions can be viewed as an input applied to a device, while the output can be any observable
property signaling the interaction. Accordingly, supramolecular interactions can be used to implement the Boolean logic
and operate in a binary system 0,1. In the chemical analogy, the actuation of an input can be viewed as the state 1 and
its lack as the state 0. On the chemical basis, all the logic functions YES, NOT, AND, OR, NOR, NAND, INHIBIT, and
XOR (Fig. 43) have been defined by means of supramolecular operations involving various chemical species, including
metal ions [111,112,166–170]. For example, the simplest YES gate (output of 1 or 0 when the input is 1 or 0,
respectively) can be generated with complex 17 using a redox potential as the input and luminescence as the output
(Fig. 44). Complex 17 is poorly emissive, due to a quenching process occurring via photoelectron transfer from the
ruthenium-based lumophore to the benzoquinone unit. However, a sixfold luminescence enhancement is obtained upon
application of a _0.6 V potential (vs SCE) in wet acetonitrile to give the fully reduced hydroquinone form, that can be
reset to 17 by application of a +1.1 V potential [170]. Starting from simple systems, like the one just described, a variety
of approaches were developed to construct molecular logic gates and systems of greater complexity.
Many examples, including Half-Adders, Half-Subtractors, Full-Adder, Full-Suntractor, encoder-decoder and set-reset
systems can be found in the cited literature [111,112,166–170].
Supramolecular chemistry has become more and more successful and it is now widely applied by researchers across
various scientific fields and disciplines. Metals have contributed substantially to such success, as testified by the number
of papers published about the use of metals in supramolecular chemistry. A search of the literature, performed at the
beginning of 2014 through SciFinder by using ‘‘supramolecular’’ as the first research topic and ‘‘metal’’ as a refinement
topic, furnished over 10000 references, about 1000 of which refer to 2013. For this reason it is impossible to construct a
comprehensive review of the area, which somehow is a credit to the many advances made in this field. Accordingly, we
have described here only some of the steps that supramolecular chemistry have moved forward, with the help of metals,
to get to the central position it now occupies on the stage of modern science and technology.
It is evident that the molecular-level understanding of the possible functions of metals in supramolecular chemistry has
created a vast array of phenomena and applications, opening the door to many future developments. For example,
applications of metalbased supramolecular chemistry may include the preparation of new nanomaterials, such as hybrid
metal–organic compounds, bio-inspired fibers and tissues, self-healing materials, molecular magnets, nanoparticles,
molecular wires (conductors and semiconductors), molecular and nano-scale electronic components, molecular
memories, molecular and nanosized devices, motors and machines. They can also contribute to medical issues, as
fundamental constituents in new treatments for diseases, for the control of protein–protein interactions and transport
channels, in new methods for tissue, organ and metabolism imaging, in intracellular drugs and contrast agents on
demand delivery, as well as they can contribute to environmental issues providing new concepts for prevention and
remediation, waste management, and solar energy capture and conversion.