Phthalocyanines:

From Molecular Structures to Solid-state Arrangements

Dr. Michael Klaus ENGEL (michael-engel@ma.dic.co.jp)

Dainippon Ink & Chemicals, Inc.Central Research Laboratories; Sakura-shi, Japan

Classification of Phthalocyanine Molecular Structures

Arrangement of the Phthalocyanine Units in Solid-state

Start: Basic information about Phthalocyanine Molecular Structures

Phthalocyanines

Molecular properties Solid-state properties PcCu -PcCu is greenish blue -PcCu is reddish blueStructure-Property Relationships

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Molecular Structures: BasicsX=CH: Tetrabenzoporphyrin: TBPH2

1) 139.0 pm 2) 249.5 pm; 127.9°3) 295.5 pm4) 688.6 pm

X=N: Phthalocyanine: PcCo1) 131.7 pm2) 229.7 pm; 121.5° 3) 269.8 pm 4) 670.5 pm

Most of the metallic elements and semimetals can be coordinated in the center of the macrocycle.Molecular structure is influenced by- the size of the central atom M, - the oxidation state of the central atom M.Two kinds of molecular axes:- bridging-nitrogen molecular axis (Nbr)- isoindole-nitrogen molecular axis (Ni)

N

N

X

N

X

N

X

XM

4

1

23

Nbrmolecularaxis

Nimolecularaxis

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Molecular Structures: BasicsCoord.Nr. Oxid.Nr. Geometry Mol.Sym. Expl.

4 2 square planar

D4h PcCu

5 2, 3, 4, 5 square pyramidal

C4vPcSn

PcAlClPcTiOPcReN

6tr 4, 5, 6 octahedral OhPcSiCl2

PcMoOCl

6cis 4 trigonal prismatic

D3hPcNbCl2

7cis 5 capped trigonal prismat

ic

C2v PcNbCl3

8cis/8bis 3, 4 cubic Oh [Pc2La]-

8cis/8bis 3, 4 square antiprismatic

D4d Pc2Zr

NN

NN

NN

NN

X

NN

X

NN

X

N

X

NN

N

X

X

NN

NN

XX

N

NN

N

N

N

N

N

NN

N

N

N

N

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Molecular Structures: MonomersMonomeric phthalocyanines with planar macrocycle and identical faces

Monomeric phthalocyanines with bent macrocycle and different faces

CN6cis

CN7cis CN8cis

CN6trCN1 CN4

CN5 CN5

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Molecular Structures: Dimers

H

Bis- and trisphthalocyanines with bent macrocycles

Dimeric phthalocyanines with planar or bent macrocycles

CN8bis CN8bis CN8bis

CN6tr

CN6cisCN7cis

CN5 CN5

CN8cis

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Increased possibilities of interactions

N

N

N

N

N

N

N

NM

Phthalocyanines additional interactionpossibilities due to the presence of heteroatoms.

Hydrogen atoms electronegative atomsNitrogen atoms hydrogen atoms axial ligands central atomsCentral atoms and axial ligands central atoms axial ligands nitrogen atoms

Aromatic hydrocarbons:Interaction between aromatic macrocycles: interactions and H- interactions

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Arrangements: Group CN4 (PcM)

4 Basic overlap geometries

-PcPt -PcH2 -PcCu x1-PcH2

overlap along Nbr molecular axis overlap along Ni molecular axis

intermolecular bonding between Nbr and center stabilizes -polymorphs

the big confusion

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Arrangements: Group CN4 (PcM)

Orientation of phthalocyanines in neighboring columns

-PcPt

-PcH2

-PcCu

x1-PcH2

S2 screw axisIntercolumnar hydrogen-bonding

intercolumnar distancesN…H > 3.2 Åmuch weaker bonding

2.7044 Å

2.6465 Å

Herringbone stacking

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Arrangements: Group CN4 (PcM)

x1-PcH2

-PcPt -PcH2

-PcCu

-PcPt

x2-PcH2 x1-PcH2

(Nbr)

(Ni)

2.6134 Å3.0143 Å 3.0499 Å

2.8408 Å

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Arrangements: Group CN6tr (PcMX2)

x1-PcH2

overlap in CN4

PcSnI2 PcCoCl2 PcSnI2

much smaller in CN6tr

spatial need of axial ligandsIntermol. hydrogen bonding+ repulsive interaction

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Arrangements: Group CN6tr (PcMX2)

x1-PcH2

Network structure view along the column axes

Network structure view along the column axes

Intercolumnar hydrogen bonding

-PcGe(OH)2

-PcGe(OH)2 2.592 Å

2.568 Å

Intercolumnar hydrogen bonding

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Molecular Structures: Group CN5 (PcMX)

M

Ni

N

Ni

NNi

N

NiN

Ca

Ca

Lax

Ni-MNi-Ctr

MNi Ni CC

= 180o isoindole unit

Why do some phthalocyanines have a saucer-shaped macrocycle ?

convex face

concave face

2 different faces each face leads to a different arrangement

MNi Ni CC

180o

turn around axisthrough C

MNi Ni CC

saucer-shaped

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Arrangements: Group CN5 (PcMX)concave convex

sheet-type (or brickstone) arrangementcolumnar (slipped-stacked) arrangements

layer-type arrangements

Ni Nbr no shift

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Arrangements: Group CN5 (PcMX)

molecular lego

concavelayer-type convex

+

+

+

PcGaCl

PcAlCl

PcZnCl

Ni

Nbr

no shift

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Hydrogen bonding

PcSn

PcNbCl2 PcSnCl2

molecular deformation through hydrogen-bonding

flattening throughrepulsive interaction

parallel not parallel ca. 3.5 Å hydrogen bondingI-PcTiO orientation through hydrogen-bonding

2.746 Å2.736 Å

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Mol. Structures: Group CN8bis (Pc2M)

N

N

N

N

N

N

N

N

N

N

N

N

NN

N

M

N

M

CCDC Molecule spacegroup angle [˚]

DPCYTH03 Pc2Th C2/c 37

DPCYTH Pc2Th C2/c 38

PHALCU* Pc2U C2/c 37

JONZAN Pc2Ce C2/c 38

SNPTCY01 Pc2Sn C2/c 38

DPCYTH01 Pc2Th C2/c 38

CIZGIB02 Pc2Nd {} C2/c 38

GAWBEL Pc2Gd P212121 ca. 41

ZAKZOA Pc2In P212121 41.2

DULZAL Pc2Lu {} P212121 41

GAWBAH Pc2LuH P212121 41

SNPTCY Pc2Sn P212121 42

YUHSUP Pc2Er {} P4/nnc 41.4

CIZGIB08 Pc2Nd P4/nnc 41.3

KOBRUO02 Pc2Pr P4/nnc 41.7

ZUWDAW [Pc2Bi][CH2Cl2] Pnma 45

ZEHTUB [Pc2La][CH2Cl2] Pnma 45

DICBUM [Pc2Lu][CH2Cl2] Pnma 45

JUVJIT [Pc2Y][CH2Cl2] Pnma 45

until now: defined by staggering angle but: angle depends on which units are used

angle corresponds to crystal structure

staggering angle is not amolecular property

bisphthalocyanines

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Arrangements: Group CN8bis (Pc2M)

A 1

1

2

2

A1

A2

-Pc2Pr

Pc2Ce

-Pc2Er

[Pc2Lu][CH2Cl2]

12

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Arrangements: Group CN8bis (Pc2M)

-Pc2Pr (A1)Pc2Ce (A2) [Pc2Lu][CH2Cl2]

(12)

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Final remarks

Further reading:M.K. Engel, J. Porph. Phthalocyanine, in preparationM.K. Engel, in "The Porphyrin Handbook",Vol. 20, 2003, 1-246P. Erk et al., CrystEngComm, 2004, accepted

The central atom together with axial ligands controlsmolecular structure and arrangement in the solid-state.

Phthalocyanines like to slip-stack.

Hydrogen-bonding is a major force.

Molecular properties (deformation) depend on the crystal arrangementcalculation of crystal structures need to use non-rigid molecules

This talk covered only pure materials, no mixtures. Co-crystallizingmaterials (impurities, solvents) can strongly influence the crystalstructure.

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Thank you

To you for listening.

To Prof. Heiner Homborg for many discussions and giving me accessto his unpublished crystal structures.

To Dr. Peter Erk for preprints and unpublished structures.

To Prof. Bob Scheidt for his work in porphyrin crystal structures whichgave me many ideas for phthalocyanine crystal structures.

To Dainippon Ink and Chemicals for having interest in my phthalocyanineresearch and allowing me to participate at this conference.

Michael Klaus Engelmichael-engel@ma.dic.co.jp

http://phthalo.mkengel.de/pcrev.htm

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