Alberto CrediCenter for Light Activated NanostructuresDipartimento di Scienze e Tecnologie Agro-alimentari, Università di Bologna, and Istituto per la Sintesi Organica e la Fotoreattività,Consiglio Nazionale delle Ricerche, Bologna, Italy

alberto.credi@unibo.it www.credi-group.it

Photoactivenanoscaledevicesandmachines

XIInternationalSchoolofOrganometallic ChemistryFromTheory toApplications

SanBenedettodelTronto,2-6September 2017

Weigth: ca.30tN.tubes: 19000Powerconsumption: 200kW

ENIAC:thefirstelectroniccomputer(1944) Integratedmicroprocessor(today)

Weigth: ca.2kgPowerconsumption: ca.60W(CPU)

N.transistors: 1.4billions*Elementssize(min): 25nm*

* Intel i7 quad core processor (22-nm lithography), released Q3 2013. See http:\\ark.intel.com

Whyminiaturization?

Wiley,New

York,200

4Cells have hundreds of different types of molecular motors, each specialized for a particular function.Many biological motor-like proteins have been discovered and characterized in recent years.

Naturallyoccurringmolecularmachines

molecularcomponents

simple acts

multicomponent(supramolecular)

system

function

V. Balzani, A. Credi, M. Venturi, PNAS 2002, 99, 4814; Chem. Eur. J. 2002, 8, 5524

Artificialmoleculardevices

M. Fujita et al. J.F. Stoddart et al.

J.-P. Sauvage et al.

Complexsyntheticstructures

ENERGY FUNCTION

MonitoringsignalsLight

Artificialmoleculardevices:theroleoflight

Multicomponent(supramolecular)

system

SUN

livingmatter

photosyntheticprocesses

vision-relatedprocesses

ENERGYfor life

INFORMATIONfor life

• Devices forsignal (information)processingWires,plug/socket devices,electrical extension cable systems,antennas,sensors,switches,logic gates,...

•Mechanicaldevices(molecularmachines)Tweezers,shuttles,muscles,valves,rotarymotors,...

• DevicesforharvestingandconvertinglightenergyLightharvestingantennas,wires,charge-separationdevices,...

Artificialmoleculardevices

Wiley-VCH, Weinheim, Germany, 2003

Wiley-VCH, Weinheim, Germany, 2008

Mechanicalmolecularmachines

D.A.Leighetal.Angew.Chem.Int.Ed. 2007,46,72Chem.Rev. 2015,115,10081

S.Silvi,M.Venturi,A.Credi,J.Mater.Chem. 2009,19,2279;Chem.Commun. 2011,47,2483(featurearticles)

C.Bruns,J.F.Stoddart,TheChemistryoftheMechanicalBond–FromMoleculestoMachines,Wiley,NewYork,2016

Informationprocessingdevices

A.P.deSilva,S.Uchiyama,NatureNanotech. 2007,2,399

K.Szacilowski, Chem.Rev. 2008,108,3481

V.Balzani,A.Credi,M.Venturi, Chem.Eur.J. 2008,14,26

A.P.deSilva,MolecularLogic-basedComputation,RSCPublishing,Cambridge,2012.

Artificialmoleculardevices

Informationprocessingdevicesbasedontransitionmetalcomplexes

N N

N

N

Ru2+ N N

N

N

Ru

N N

N

N

Ru2+ N NH+N

N

+HN N

N

N

Ru2+ N NH+N

N

+ H+

+ H+

- H+

- H+

RuH+

RuH22+

Inorg.Chim.Acta 2007,360,1102

l (nm)

600 650 700 750 800 850 900

I (a.u.)

0.0

0.4

0.8

1.2

l (nm)

300 400 500 600 700 800

Abs

0.0

0.3

0.6

0.9

eq acid0 1 2 3 4

A498

0.30

0.35

MeCN, RT

PaoloPassaniti,SerenaSilvi WithEdConstable,UniversityofBasel

Anacid-basecontrolledluminescentswitch

0 0 0 0 1

0 1 0 1 0

1 0 0 1 0

1 1 1 1 1

In1 In2 Out740 Out740 Out630In1 = H+

In2 = H+

Out = hn

AND

OR

XNOR

AND

OR

XNOR

Ru

RuH+

RuH22+

NH+

MH+

hn

DA (stateA)

DB (stateB)

+H+ – H+

Molecular Switch2Molecular Switch1

- pKa(NH+)<pKa(DA)<pKa(MH+)

- compatibilityofconditions- nofurtherchemicalinteractionsbetweenMS1andMS2

- nointerferenceofinput/outputsignals- correcttimingoftheswitchingprocesses

communicationofachemicalsignal(H+ ions)

PhotochemicaloperationofpH-controlledmolecularswitches

N O NO2

OHSP

+H+,dark

Visible LightN+

OH

HO

NO2

MEH+

l (nm)300 400 500 600

A

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

SP

MEH+

MeCN, RT

SerenaSilvi

Thespyropyran/merocyanine photochromicsystem

WithFrançisco Raymo,UniversityofMiami

l / nm

600 700 800 900

I

0

1

2

3

4

5

+HN N

N

N

Ru2+ N NH+N

N

N O NO2

OH

2SP

N N

N

N

Ru2+ N N

N

N

Ru RuH22+

2H+

D

2H+hn

2N+

OH

HO

NO2

2MEH+

2

MeCN, RT

Coupledoperationofthetwoswitches

+HN N

N

N

Ru2+ N NH+N

N

N O NO2

OH

N N

N

N

Ru2+ N N

N

N

2

++

N N

N

N

Ru2+ N NH+N

N

SP MEH+

++

D

D

+hn

++hn

2

MeCN, RTChem.Eur.J. 2009,15,178

Photocontrol ofmolecularlogicgateoperation

630 nm 740 nm

I

0

1

2

3

4

00 10 00 01 00 11

0 0

0 1

1 0

1 1

In1 In2 Out

0

0

0

1

AND

Out

0

1

1

1

OR

Lum

ines

cenc

e in

tens

ity (a

.u.)

Chem.Eur.J. 2009,15,178

I

0.0

0.1

0.2

0.3

0.4

00 10 00 01 00 11

0 0

0 1

1 0

1 1

In1 In2 Out

1

0

0

1

XNOR

630 nm 740 nm

Chem.Eur.J. 2009,15,178

Lum

ines

cenc

e in

tens

ity (a

.u.)

Luminescenceof the Oscomplex

1O2 luminescence

Chem.Commun. 2009,1484

lirr = 450 nm

t = 120 ns t = 20 ns

Photochemicalswitchingofluminescenceand1O2 generation

Nanoscale devicesbasedonsemiconductornanocrystal quantumdots