Supplementary Information
DirectImagingofPrecursor

Adcomplex

StatesduringCryogenic-Temperature On-Surface Metalation: Scanning Tunneling Microscopy Studyon Porphyrin Array with Fe Adsorption at 78.5 KEiichi Inami1,2*, Masataka Yamaguchi1, Ryohei Nemoto1, Hideki Yorimitsu3, Peter Krüger1,4,and Toyo Kazu Yamada1,4*

1. Department of Materials Science, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan.
2. School of Systems Engineering, Kochi University of Technology, 185 Miyanokuchi, Tosayamada, Kami,Kochi 782-8502, Japan
3. Department of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa, Oiwakecho,Sakyo-ku, Kyoto 606-8502, Japan.
4. Molecular Chirality Research Center, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan.

Author Information,
Corresponding Author: Eiichi Inami *E-mail: inami.eiichi@kochi-tech.ac.jp
Corresponding Author: Toyo Kazu Yamada *E-mail: toyoyamada@faculty.chiba-u.jp

S1

Tunneling current maps (I(V) maps) of Fe atom adsorption on 2HTPP at 78.5 K in UHV.

Topography

I(V) maps-1.4 V-1.3 V-1.2 V-1.1 V-1.0 V-0.9 V-0.8 V-0.7 V-0.6 V-0.5 V-0.4 V-0.3 V-0.2 V-0.1 V

0V

0.1 V

0.2 V

0.3 V

0.4 V

0.5 V

0.6 V

0.7 V

0.8 V

0.9 V

1.0 V

Figure S1. STM topography (30 × 30 nm2, Vs = –1400 mV, It = 500 pA) and simultaneously recorded
CITS current images (from –1.4 V to +1.0 V) obtained on the H2TPP monolayer films on Au(111)
surface after deposition of ~0.05 ML of Fe atoms.

S2

Differential conductance maps (dI/dV maps) of Fe atom adsorption on 2HTPP at 78.5 K in UHV.

Topography

30rm
corresponding
Vmonolayer
deposition
analyticallyindI/dV maps
-1.4 V-1.3 V-1.2 V-1.1 V-1.0 V-0.9 V-0.8 V-0.7 V-0.6 V-0.5 V-0.4 V-0.3 V-0.2 V-0.1 V

0V

0.1 V

0.2 V

0.3 V

0.4 V

0.5 V

0.6 V

0.7 V

0.8 V

0.9 V

1.0 V

Figure S2. STM topography image (30 × 30 nm2, Vs = –1400 mV, It = 500 pA) and simultaneously
recorded CITS differential conductance dI/dV maps (from –1.4 V to +1.0 V) obtained on the H2TPP
monolayer films on Au(111) surface after deposition of ~0.05 ML of Fe atoms.

S3

DFT calculation results of 2HTPP, FeTPP, and Fe-2HTPP adcomplex.

2HTPP
2HTPP

DOS

FeTPP

FeTPP

Fe-2HTPP adcomplex

Fe-2HTPP adcomplex

E – EF [eV]
Figure S3. DFT calculated DOS of 2HTPP [red line], FeTPP [dotted line] and Fe-2HTPP adcomplex[black line]. Right panels denote models of calculated molecular structures: 3D and top views.

S4

DFT calculation results of two types of Fe-2HTPP adcomplex.

Fe-2HTPP_H_upup

DOS

Fe-2HTPP_H_upup

Fe-2HTPP_H_updown

Fe-2HTPP_H_updown

E – EF [eV]

Figure S4. DFT calculated DOS of two types of Fe-2HTPP adcomplex. Type A [black line]: twohydrogen atoms at the core position point upwards. Type B [grey line]: one of the two hydrogenatoms at the core position points upwards, while other points downwards. Right panels denote modelsof calculated molecular structures: 3D and top views.

S5

STM topographic images of one monolayer (ML) H2Pc film grown on Cu(111) before and after
the 0.1 ML Fe deposition at 300 K in UHV.

One monolayer H2Pc / Cu(111)

0.1 ML Fe deposition on 1 ML H2Pc / Cu(111)100×100 nm2, 1.2 V, 15 pA

50×50 nm2, -1.5 V, 15 pA

Figure S5. Left panel: STM topographic image obtained on a one monolayer (ML) metal-freephthalocyanine (H2Pc) film grown on Cu(111). Brigit dot array denotes a molecular lattice. Rightpanel: STM topographic image obtained on the 1 ML H2Pc film on Cu(111) after 0.1 ML Fe
deposition at 300 K. These experiments were supported by Mr. Yuta Sakai.

S6